JP2016211003A - Two-pack type curable polyorganosiloxane composition for semiconductor light emitting device, polyorganosiloxane-cured article obtained by curing the composition and production method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-pack type curable polyorganosiloxane composition for a semiconductor light emitting device member, excellent in storage stability, light resistance and adhesiveness as a liquid and having sufficient heat resistance, hydrothermal resistance and film deposition property.SOLUTION: There is provided the two-pack type curable polyorganosiloxane composition for a semiconductor light emitting device member, having following liquid composition (A) and liquid composition (B). The liquid composition (B) contains a polyorganosiloxane compound preferably containing in a molecule, two or more of substituents which react with a silanol group, and further preferably the substituents which react with the silanol group being at least one kind of organic acid containing a hydrosilyl group, the silanol group and a hydroxyl group. The liquid composition (A): a liquid composition containing a polyorganosiloxane compound having two or more silanol groups in a molecule and practically no condensation catalyst. The liquid composition (B): a liquid composition containing a condensation catalyst and practically no Pt.SELECTED DRAWING: None

Description

  The present invention relates to a novel two-component curable polyorganosiloxane composition for a semiconductor light-emitting device member, a cured polyorganosiloxane obtained by curing the composition, and a method for producing the same. Furthermore, the present invention relates to the cured polyorganosiloxane, a method for producing the same, an optical member, a member for aerospace industry, a semiconductor light emitting device, a lighting device, and an image display device using the cured polyorganosiloxane. .

  In a semiconductor light emitting device such as a light emitting diode (hereinafter abbreviated as “LED” as appropriate) and a semiconductor laser, the semiconductor light emitting element is sealed with a member such as a transparent resin (optical member for a semiconductor light emitting device). Things are common. As the optical member for the semiconductor light emitting device, an epoxy resin is mainly used, and the emission wavelength from the semiconductor light emitting element is converted by including a pigment such as a phosphor in the epoxy resin or the like. Things are known.

However, since epoxy resin has high hygroscopicity, when a semiconductor light-emitting device is used for a long time, (i) cracks are generated by heat from the semiconductor light-emitting element, and (ii) phosphor and light-emitting element are deteriorated due to moisture penetration. There were issues such as.
In addition, in recent years, the epoxy resin has deteriorated and colored with the shortening of the emission wavelength of the LED, so that there has been a problem that the luminance of the semiconductor light emitting device is remarkably lowered when used for a long time and at a high output. .

  In response to these problems, silicone resins having excellent heat resistance and ultraviolet light resistance have been used as substitutes for epoxy resins. That is, a semiconductor light emitting device using a silicone resin (polyorganosiloxane composition) as a material excellent in heat resistance and ultraviolet light resistance has been proposed (see, for example, Patent Documents 1 to 6).

JP 2006-077234 A JP 2006-291018 A JP 2006-294821 A International Publication 2006/090804 Pamphlet Japanese Patent No. 327749 JP 2009-256670 A

  In particular, Patent Documents 1 to 4 describe curable resin compositions for sealing LED elements using specific polyorganosiloxanes. The polyorganosiloxanes described in Patent Documents 1 to 4 have improved film formability compared to glass materials using only tetrafunctional silicon by adjusting the degree of crosslinking by introducing organic groups. However, the amount of trifunctional or higher functional silicon used as a crosslinking component is large, and the cured product is hard and brittle glass. For this reason, when applied to a large-sized semiconductor light-emitting device such as a power LED, the stress cannot be relieved at the adhesion interface with the LED chip or reflector, and the sealing material is liable to peel off during long-term lighting use or thermal shock such as reflow. There was a problem.

  In addition, the present inventors disclosed a specific member for a silicon-containing semiconductor light-emitting device in Patent Document 4 that can solve the above problems. However, in semiconductor light-emitting devices that use short-wavelength LEDs in the near-ultraviolet to ultraviolet region, deterioration such as coloring is likely to occur. Therefore, it has been desired to impart light resistance to such short-wavelength light. In addition, when used for a semiconductor power device that further dissipates heat, it has been desired to further increase the level of heat and hydrothermal stability while maintaining light resistance, film formability, and adhesion. In particular, in the case of a composition containing a phosphor, heat stability is required to maintain the luminance of the phosphor even when used for a long time and at a high output. In addition, it has been desired to suppress the volatilization of low boiling impurities in the manufacturing process of the semiconductor light emitting device member and to improve the weight yield of the cured product.

Moreover, although the polyorganosiloxane composition of patent document 5 is a gel-like substance which can be used as a resin composition for LED element sealing, the gel-like thing does not stabilize the property at the time of LED lighting, and protects a light emitting element. In view of the fact that the sealing curable resin composition should fulfill this purpose, it cannot be said to be suitable. Furthermore, since the system is internally cured by a dehydrogenation type reaction, there is a decisive problem that foaming occurs due to the influence of by-produced hydrogen gas. Since this foaming causes the following problems, a means for solving this problem has been desired.
(I) When used as a sealing material for a semiconductor light-emitting device, a problem of peeling occurs due to foaming present at the interface between the sealing material and other members.
(Ii) When foaming occurs at the interface of the phosphor and other members, the heat transfer property that releases heat from the LED chip by the air being foamed is reduced, and the phosphor and other members are liable to deteriorate.
(Iii) Excitation light of the light emitting element is easily lost due to the influence of bubbles, and the light conversion efficiency is significantly reduced.
(Iv) It is difficult to always make a uniform product.

  In addition, the present applicant disclosed in Patent Document 6 a specific polyorganosiloxane composition that can solve the above-mentioned problems. However, when the composition of Patent Document 6 is stored in a single liquid state and used for a semiconductor light emitting device, there is a problem in storage stability because of high catalytic activity, which tends to increase viscosity. Further, in order to ensure storage stability, the polyorganosiloxane composition of Patent Document 6 is stored in two liquids of (A) a polyorganosiloxane component having a silanol group and (B) a polyorganosiloxane having a hydrosilyl group. When a catalyst component is added to (A), there is a problem that a condensable group reacts during storage and thickens or moisture is generated in the system. On the other hand, when a catalyst component is added to (B), (B) reacts with moisture in the environment to generate hydrogen and produce silanol groups to increase the viscosity during storage, or the liquid is colored by the interaction between the catalyst and (B). There was a problem to do.

From the background described above, the semiconductor light emitting device has excellent light resistance (particularly UV resistance) and adhesiveness, sufficient heat resistance and film formability, and does not cause cracking, peeling or coloring even after long-term use. Therefore, there has been a demand for an optical member that can be sealed with a high luminance retention rate when a phosphor is contained. In addition, it has excellent storage stability as a liquid, has less foaming when cured as a sealing material, and can be a semiconductor light-emitting device with good light guiding properties and little deterioration, and high brightness when containing a phosphor. There has been a demand for an optical member capable of maintaining the maintenance rate for a long period of time.
Further, from the viewpoint of productivity, a curable composition for a semiconductor light-emitting device member that can be cured in a shorter time than a conventional condensation-type silicone material in addition to the above performance has been demanded.

  The present invention has been made in view of the above-described problems. That is, the object of the present invention is excellent in light resistance (particularly UV resistance) and adhesion, and has sufficient heat resistance, hydrothermal resistance and film formability, excellent storage stability as a liquid, and further cured. An optical member capable of sealing a semiconductor light emitting device without causing foaming, cracking, peeling, coloring or foaming even when used for a long period of time, and having a high luminance maintenance rate when containing a phosphor, An object of the present invention is to provide a curable polyorganosiloxane composition that is an optical member forming liquid for forming, and a member for aerospace industry, a semiconductor light emitting device, a lighting device, and an image display device that make use of its excellent characteristics.

  As a result of intensive investigations to improve the storage stability of the polyorganosiloxane composition in particular, the present inventors have obtained a liquid composition (A) containing a specific silanol group-containing polyorganosiloxane compound from which the condensation catalyst has been removed. And a two-component curable polyorganosiloxane composition having a liquid composition (B) which is a specific liquid composition containing a condensation catalyst. And it discovered that this 2 liquid type curable polyorganosiloxane composition was excellent in the storage stability at the time of storing two liquid compositions, respectively. Moreover, it discovered that the hardened | cured material was excellent in not only light resistance but adhesiveness, and also had extremely high heat resistance and hydrothermal resistance compared with the past, and also had favorable film formability. Furthermore, it has been found that when this two-component curable polyorganosiloxane composition is cured by containing a phosphor, an optical member for a semiconductor light emitting device having a high luminance maintenance ratio can be obtained.

  Further, this two-component curable polyorganosiloxane composition for semiconductor light emitting device members and the cured product thereof are suitable not only as a sealing material but also as a package material and adhesive (dibon agent, etc.) for semiconductor light emitting devices. Found to be used. Further, the two-component curable polyorganosiloxane composition and the cured product thereof are not only used in the semiconductor light emitting device field, but also have light transmittance (transparency), light resistance, heat resistance, hydrothermal resistance, and UV resistance. It has been found that the present invention has applicability to materials for aerospace industry and other materials that require various characteristics such as.

That is, the present invention relates to the following [1] to [17].
[1] A two-component curable polyorganosiloxane composition for a semiconductor light-emitting device member having the following liquid composition (A) and liquid composition (B).
Liquid composition (A): a liquid composition containing a polyorganosiloxane compound containing two or more silanol groups in one molecule and substantially free of a condensation catalyst Liquid composition (B): containing a condensation catalyst And a liquid composition substantially free of platinum (Pt) [2] The liquid composition (B) contains a polyorganosiloxane compound containing two or more substituents that react with silanol groups in one molecule. The two-component curable polyorganosiloxane composition according to [1].
[3] The two-component curable polyorganosiloxane composition according to [2], wherein the substituent that reacts with the silanol group is at least one selected from a hydrosilyl group, a silanol group, and an organic group containing a hydroxyl group. object.
[4] The two-component curable polyorganosiloxane composition according to [2] or [3], wherein the polyorganosiloxane compound in the liquid composition (B) is a compound represented by the following general formula (1): .
(In the general formula (1), R ^{1 to} R ³ and R ^{5 to} R ⁸ are each independently a group selected from a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and R ¹⁰ R ¹¹ R ¹² SiO. R ⁴ and R ^{9 to} R ¹² each independently represents a group selected from a hydrogen atom, an alkyl group, an alkenyl group and an aryl group, l is an integer of 2 or more, and m is an integer of 0 or more. Is shown respectively.)
[5] The two-component curable polyorganosiloxane composition according to any one of [1] to [4], wherein the liquid composition (A) contains a compound represented by the following general formula (2).
(In the general formula (2), R ^{13 to} R ¹⁸ each independently represents a group selected from a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group and an aryl group. Moreover, p, q and r are Represents a number greater than or equal to 0, and p + q + r = 1.)
[6] The two-component curable polyorganosiloxane composition according to any one of [1] to [5], wherein at least one of the liquid composition (A) and the liquid composition (B) further contains inorganic particles. .
[7] The two-component curable polyorgano described in any one of [1] to [6], wherein at least one of the liquid composition (A) and the liquid composition (B) contains a silicone-based crosslinking accelerator. Siloxane composition.
[8] The two-pack type curable polycrystal according to the above [7], wherein the silicone-based crosslinking accelerator is an organosiloxane oligomer containing trifunctional or higher functional silicon, and the oligomer has a weight average molecular weight of 200 to 100,000. Organosiloxane composition.
[9] The two-component liquid according to [7] or [8], wherein the content of the silicone-based crosslinking accelerator is in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the liquid composition (A). Type curable polyorganosiloxane composition.
[10] The two-component curable polyorgano described in any one of [1] to [9], wherein the liquid composition (A) is obtained by removing the condensation catalyst using an adsorbent substance. Siloxane composition.
[11] A step of mixing and curing the liquid composition (A) and the liquid composition (B) in the two-component curable polyorganosiloxane composition according to any one of [1] to [10]. A method for producing a cured polyorganosiloxane.
[12] A cured polyorganosiloxane obtained by curing the two-component curable polyorganosiloxane composition according to any one of [1] to [10].
[13] An optical member comprising the cured polyorganosiloxane according to [12].
[14] A member for aerospace industry containing the cured polyorganosiloxane according to [12].
[15] A semiconductor light emitting device comprising the optical member according to [13].
[16] An illumination device comprising the semiconductor light emitting device according to [15].
[17] An image display device comprising the semiconductor light emitting device according to [15].

  The two-component curable polyorganosiloxane composition for a semiconductor light-emitting device member of the present invention is excellent in storage stability of each of the liquid composition (A) and the liquid composition (B) and foamed when the two components are mixed. The cured polyorganosiloxane, which is a cured product, is excellent in light transmittance (transparency), heat resistance, light resistance, hydrothermal resistance, and UV resistance. Therefore, the cured polyorganosiloxane of the present invention has high light transmittance (transparency), light resistance, heat resistance, hydrothermal resistance, etc., and foaming is suppressed, so that it can be suitably used for various optical members. it can.

  For example, the optical member can be suitably used for a semiconductor light emitting device, a light guide plate, and a waveguide. Furthermore, since the two-component curable polyorganosiloxane composition for semiconductor light-emitting device members and the optical member of the present invention have high hydrothermal resistance, UV resistance, etc. in addition to the above-described characteristics, these various characteristics are also exhibited. It can also be applied to required materials, for example, materials for devices using semiconductor light emitting elements (ultraviolet to near ultraviolet LEDs) that emit light in the ultraviolet to near ultraviolet region, materials for aerospace industry, and other materials.

1 is a schematic cross-sectional view showing a first embodiment. FIG. 6 is a schematic cross-sectional view showing a second embodiment. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 1. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 2. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 3. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 4. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 10. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 11. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 12. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 17. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 18. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Example 10-2. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 3.

  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.

[1] Two-part curable polyorganosiloxane composition for semiconductor light-emitting device member Two-part curable polyorganosiloxane composition for semiconductor light-emitting device member of the present invention (hereinafter, “the curable polyorganosiloxane composition of the present invention” Or simply “two-component composition of the present invention”) is characterized by having the following liquid composition (A) and liquid composition (B).
Liquid composition (A): a liquid composition containing a polyorganosiloxane compound containing two or more silanol groups in one molecule and substantially free of a condensation catalyst Liquid composition (B): containing a condensation catalyst In addition, a liquid composition that does not substantially contain Pt is a two-part composition. Two kinds of liquid compositions are stored separately, and the two kinds of liquid compositions are mixed at the time of use and cured by a curing reaction. A thing that gets things. That is, in the two-part composition of the present invention, the liquid composition (A) and the liquid composition (B) exist separately during storage, and these are mixed during use such as sealing a semiconductor light emitting device. The desired cured product (polyorganosiloxane cured product) is obtained.
Hereinafter, the two-component composition of the present invention will be described in detail.

[1-1] Liquid composition (A)
[1-1-1] Polyorganosiloxane compound containing two or more silanol groups in one molecule The liquid composition (A) according to the present invention is a polyorganosiloxane containing two or more silanol groups in one molecule. A compound (hereinafter sometimes referred to as “polyorganosiloxane compound (a)”). The polyorganosiloxane compound (a) containing two or more silanol groups in one molecule is a component that contributes to the condensation reaction by mixing with the liquid composition (B) described later in the liquid composition (A), or The polyorganosiloxane compound (b) contained in the liquid composition (B) described later acts as a crosslinking agent for curing the composition by a condensation reaction.
By containing two or more silanol groups in one molecule, it becomes possible to increase the molecular weight linearly and three-dimensionally while reacting with a trifunctional molecule and crosslinking.
In addition, when components other than the condensation catalyst of liquid composition (B) are volatile organic solvents, and the component contained in liquid composition (B) does not participate in bridge | crosslinking with a polyorganosiloxane compound (a). The liquid composition (A) itself can be three-dimensionally crosslinked and cured, that is, it contains a branched polyorganosiloxane compound having 2 or more, preferably 3 or more silanol groups in one molecule. .

  The polyorganosiloxane compound (a) preferably contains a compound represented by the following general formula (2). The molecular structure may be any of linear, branched, and three-dimensional net.

(In General Formula (2), R ^{13 to} R ¹⁸ each independently represents a group selected from a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group, and an aryl group. P, q, and r are 0 or more. And p + q + r = 1.)
In addition, when components other than the catalyst of the liquid composition (B) do not react with the compound represented by the general formula (2) such as a volatile organic solvent, 0 ≦ p is preferable, and 0 <p It is particularly preferred that

Moreover, in the case where light resistance and ultraviolet transparency are important, among R ^{13 to} R ¹⁸ in the compound represented by the general formula (2), at least 80 mol%, preferably 95 mol% or more, more preferably 99 mol. % Or more is preferably a methyl group.

In R ^{13 to} R ¹⁸ of the general formula (2), the alkyl group, alkenyl group and aryl group may be further substituted with a halogen atom. Preferred alkyl groups, alkenyl groups and aryl groups are [1-2]. In R ^{1 to} R ³ and R ^{5 to} R ⁸ described later. Among them, those having no aliphatic unsaturated bond are preferable. Preferable examples of such substituents include a phenyl group and a methyl group.

In addition, in the silanol group polyorganosiloxane compound (a), it is important that the amount of silanol groups in the molecule is not excessive from the viewpoint of moderately suppressing an increase in viscosity during long-term storage or curing. . That is, the number of silanol groups in R ^{13 to} R ¹⁸ in the general formula (2) is usually 20% or less, preferably 10% or less, more preferably 5% or less, based on the total number of substituents R ^{13 to} R ^18. Usually, it is 0.01% or more, preferably 0.05% or more, and more preferably 0.1% or more. If the amount of silanol groups is too large, the rate of increase in viscosity is large and storage stability may be lowered, or water droplets may be generated during storage. Moreover, when there is too little quantity of a silanol group, progress of reaction may become slow or may become inadequate.

Specific examples of the polyorganosiloxane compound containing two or more silanol groups represented by the general formula (2) in one molecule include, for example, branched or unbranched hydroxy-terminated polydimethylsiloxanes. Can be mentioned. A polyorganosiloxane compound containing two or more of these hydroxyl groups in one molecule can be synthesized by polycondensing a silane / polyorganosiloxane having a hydrolyzable group. Commercially available products can also be used. Examples of hydroxy-terminated polydimethylsiloxane manufactured by Momentive Performance Materials include XC96-723, XF3905, YF3057, YF3800, YF3802, YF3807, and YF3897.
Especially, it is preferable that the liquid composition (A) contains the branched polyorganosiloxane compound containing a crosslinkable silicon.
As described later, the liquid composition (B) has a substituent that reacts with a silanol group as a crosslinkable polyorganosiloxane compound that contributes to crosslinking of the polyorganosiloxane compound (a) contained in the liquid composition (A). It may contain a polyorganosiloxane compound (hereinafter sometimes referred to as “polyorganosiloxane compound (b)”) containing two or more in one molecule. On the other hand, since the liquid composition (B) contains a condensation catalyst, if the concentration of the polyorganosiloxane compound (b) in the liquid composition (B) is too high, the crosslinking reaction proceeds and the liquid composition (B). There is a risk of excessive thickening. Here, when a branched polyorganosiloxane compound containing a crosslinkable silicon is used as the polyorganosiloxane compound (a), the content of the crosslinkable polyorganosiloxane compound (b) in the liquid composition (B) is reduced. Therefore, excessive thickening of the liquid composition (B) containing the condensation catalyst can be avoided, and the storage stability of the composition (B) can be maintained.

The weight average molecular weight in terms of polystyrene of the polyorganosiloxane compound (a) is usually 160 or more, preferably 400 or more, more preferably 500 or more, and usually 700,000 or less, preferably 50000 or less, more preferably 30000 or less. If the weight average molecular weight is too small, the polyorganosiloxane compound itself volatilizes during curing, or the condensation-reactive terminal group content increases, resulting in a decrease in weight yield during curing and the cured product shrinks. There is a possibility that internal stress is high and viscosity becomes difficult to handle.
On the other hand, when the polyorganosiloxane compound (a) is a branched polyorganosiloxane containing two or more silanol groups in one molecule, if the weight average molecular weight is too large, it is mixed with the liquid composition (B). Curing speed may be too fast. When the polyorganosiloxane compound (a) is a linear polyorganosiloxane containing two silanol groups per molecule, the liquid composition (B) contains the crosslinkable polyorganosiloxane compound (b). Although it is necessary, when the weight average molecular weight of the polyorganosiloxane compound (a) is too large, when the liquid composition (A) and the liquid composition (B) are mixed, the polyorganosiloxane compound (a) is crosslinked with the polyorganosiloxane compound (a). The reactivity with the functional polyorganosiloxane compound (b) may be low, and the liquid composition may be difficult to cure.
In the liquid composition (A), one type of polyorganosiloxane compound (a) may be used alone, or two or more types may be used in any combination and ratio.

[1-1-2] Condensation catalyst The liquid composition (A) according to the present invention does not substantially contain a condensation catalyst in order to make the storage stability of the two-component composition of the present invention effective. Is a feature. For example, when a polyorganosiloxane compound containing two or more silanol groups contained in the liquid composition (A) is obtained by a condensation reaction, from the liquid composition (A) in the condensation reaction It is necessary to remove the condensation catalyst used.

  From this point of view, “substantially does not contain a condensation catalyst” means that the liquid composition (A) does not contain “effective amount of technical common sense for those skilled in the art” in an amount that impairs storage stability. Means that. Specifically, the amount of the condensation catalyst relative to the whole liquid composition (A) is usually 80 ppm or less, preferably 40 ppm or less, more preferably 20 ppm or less in terms of metal. When the condensation catalyst is deactivated as described in (iii) below, and the remaining component derived from the condensation catalyst does not adversely affect the storage stability of the liquid composition (A), the catalyst-derived metal More components may remain than the above, and the amount thereof is usually 300 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less in terms of metal. If it exceeds this amount, the liquid composition (A) may become cloudy or the ultraviolet transparency may be impaired.

Details of the condensation catalyst will be described later in [1-2-2].
Examples of a method for removing the condensation catalyst used in the condensation reaction from the liquid composition (A) include the following methods. A method in which the catalytic metal component is not removed and the activity is lost as in (iii) can also be selected.
(I) Removal of condensation catalyst by activated carbon, porous silica, synthetic adsorbent and other adsorbents (ii) Removal of condensation catalyst by washing with water, alcohol and other solvents (iii) Neutralization, hydrolysis and reaction inhibition of catalyst components Deactivation of condensation catalyst by adding agent

[1-2] Liquid composition (B)
The liquid composition (B) is a liquid composition containing a condensation catalyst and substantially not containing Pt.
As described above, the two-component composition of the present invention is used by mixing the liquid composition (B) with the aforementioned liquid composition (A). Examples of such a liquid composition (B) include those obtained by dissolving a condensation catalyst in a liquid medium such as an organic solvent or a polyorganosiloxane compound.

  Examples of the organic solvent that can be used for the liquid medium include hydrocarbon solvents. Among these, from the viewpoint of compatibility with the siloxane compound that is the main component of the liquid composition (A), an aromatic compound having 6 to 10 carbon atoms that has no nonpolar or less polar reactive organic group, preferably toluene. Benzene, xylene, ethylbenzene, etc., or branched or unbranched chain saturated hydrocarbons having 5 to 15 carbon atoms, preferably hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, etc. it can. The components of these hydrocarbon solvents may be single or a mixture, and a mixed solvent such as gasoline or mineral spirit may be used. Among these, a chain saturated hydrocarbon solvent is particularly preferable because it has low toxicity and hardly absorbs ultraviolet light when it remains in a cured product.

  When a volatile organic solvent is used, the boiling point can be appropriately selected depending on the coating method. Usually, the organic solvent component is such that the liquid composition (B) has a boiling point of 40 to 200 ° C, preferably 50 to 150 ° C. It is preferable to select When the boiling point of the liquid composition (B) is lower than the above range, the flammability becomes high, resulting in a safety problem. When the temperature is higher than the above range, the organic solvent remains in the cured product. There is a possibility that weight loss and transmittance decrease due to heating during use.

Examples of the polyorganosiloxane compound that can be used in the liquid medium include a polyorganosiloxane compound (polyorganosiloxane compound (b)) containing two or more substituents that react with a silanol group described later in one molecule. It is done. The polyorganosiloxane compound is preferable because it does not cause problems such as bleeding out, volatilization, and weight loss after heating.
The organic solvent as the liquid medium and the polyorganosiloxane compound can be used alone or in combination.

[1-2-1] A polyorganosiloxane compound containing two or more substituents that react with a silanol group in one molecule. The liquid composition (B) preferably reacts with the silanol group of the liquid composition (A). A polyorganosiloxane compound (polyorganosiloxane compound (b)) containing two or more substituents in one molecule is contained. The polyorganosiloxane compound (b) binds to the polyorganosiloxane compound (a) containing two or more silanol groups in one molecule by containing two or more substituents that react with the silanol group in one molecule. In addition, the molecular weight can be increased in a linear manner or three-dimensionally while reacting with a trifunctional molecule and crosslinking.
The substituent that reacts with the silanol group in the polyorganosiloxane compound (b) is not particularly limited as long as it achieves the above-mentioned purpose. For example, (i) hydrosilyl group (Si-H), (ii) silanol group (Si—OH), (iii) An organic group containing a hydroxyl group (Si—R—OH), and the like.

[1-2-1-1] Hydrosilyl Group-Containing Polyorganosiloxane Compound As a preferred example of the polyorganosiloxane compound (b), a hydrosilyl group-containing polyorganosiloxane compound (hereinafter referred to as “polyorganosiloxane compound (b1)”) Can be mentioned).
Since the polyorganosiloxane compound (b1) has a hydrosilyl group in the siloxane skeleton, the crosslinking density can be adjusted. It is preferable that two or more hydrosilyl groups are contained in one molecule.
The siloxane compound containing two or more hydrosilyl groups in one molecule is a linear, branched, or three-dimensional net-like polyorganosiloxane having at least two, preferably three or more SiH bonds in one molecule. Compounds.

The polyorganosiloxane compound has a substituted or unsubstituted monovalent hydrocarbon group bonded to a silicon atom. Examples of such a monovalent hydrocarbon group usually include those having 1 to 12 carbon atoms, preferably about 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, Alkyl group such as isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl Group, aralkyl group such as phenylethyl group, phenylpropyl group, etc., alkenyl group such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group, octenyl group, and hydrogen of these groups Some or all of the atoms are substituted with halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc., such as chloro Ethyl group, chloropropyl group, bromoethyl group, and a halogen-substituted alkyl group or cyanoethyl group such trifluoropropyl group. Moreover, the C1-C3 alkoxy group within 3 wt% may be contained.
Among the above-mentioned substituents, those having no aliphatic unsaturated bond are preferable from the viewpoints of storage stability of the liquid composition (B) and light resistance and heat resistance of the resulting cured product. In the case where the light resistance is required, it is preferable that the above substituent is mainly a methyl group. Further, by allowing a phenyl group to coexist with a methyl group, the hardness, refractive index, gas permeability and the like of the resulting cured product can be adjusted.

Specific examples of the polyorganosiloxane compound include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, Both end trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, Both end dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, Both end dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, Both ends Trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer Body, (CH _{3) 2} HSiO copolymers consisting of _1/2 units and SiO _4/2 units, and, (CH _{3) 2} HSiO _1/2 units, and SiO _4/2 units (C ₆ H ₅₎ SiO _{3 A} copolymer composed of _{/ 2} units.

  Among these, a compound represented by the following general formula (1) can be preferably used.

(In the general formula (1), R ^{1 to} R ³ and R ^{5 to} R ⁸ are each independently a group selected from a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and R ¹⁰ R ¹¹ R ¹² SiO. R ⁴ and R ^{9 to} R ¹² each independently represents a group selected from a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group, l is an integer of 2 or more, and m is 0 or more. Indicates an integer respectively.)

  Hereafter, it demonstrates in detail about the compound represented by General formula (1).

(R ¹ to R ³ and R ⁵ to R ⁸⁾
As described above, R ^{1 to} R ³ and R ^{5 to} R ⁸ are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, and R ¹⁰ R ¹¹ R ¹² SiO. Show. Among these, the alkyl group, alkenyl group, aryl group, and R ¹⁰ R ¹¹ R ¹² SiO may be further substituted with a halogen atom.

Preferable alkyl groups include, for example, a methyl group, an ethyl group, a propyl group, and a trifluoropropyl group. Moreover, as a preferable alkenyl group, a vinyl group is mentioned, for example. Moreover, as a preferable aryl group, a phenyl group is mentioned, for example.
Among these, particularly preferred groups include a phenyl group and a methyl group.

(R ⁴ and R ^{9 to} R ¹² )
R ⁴ and R ^{9 to} R ¹² each independently represent a group selected from a hydrogen atom, an alkyl group, an alkenyl group, and an aryl group. The alkyl group, alkenyl group and aryl group may be further substituted with a halogen atom. Preferred alkyl groups, alkenyl groups and aryl groups are the same as those described above for R ^{1 to} R ³ and R ^{5 to} R ⁸ .
Among these, a phenyl group and a methyl group are particularly preferable.

  Specific examples of the hydrosilyl group-containing polyorganosiloxane compound represented by the general formula (1) include, for example, hydrogen terminated polydimethylsiloxanes and polymethylhydrosiloxanes trimethylsilyl terminated. Can be mentioned. Commercially available products such as KF-99 and KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., SH1107 series manufactured by Toray Dow Corning Co., Ltd., TSF484 and TSL9586 manufactured by Momentive Performance Materials, and H- manufactured by Asahi Kasei Wacker Co., Ltd. Examples include Siloxane, HMS series made by Gelest, DMS series, and the like.

The weight average molecular weight in terms of polystyrene in the hydrosilyl group-containing polyorganosiloxane compound is usually 160 or more, preferably 500 or more.
In particular, when the two-component composition of the present invention is a cured product, the weight average molecular weight is preferably 5000 or more in order to suppress shrinkage under conditions such as a temperature of 200 ° C. or higher. . Further, in order to facilitate curing after mixing the liquid compositions (A) and (B), the weight average molecular weight is more preferably 27000 or more.

  The weight average molecular weight of the hydrosilyl group-containing polyorganosiloxane compound is usually 700,000 or less, preferably 100,000 or less. Among these, in order to reduce the viscosity of the liquid composition (B) and improve the handling, the weight average molecular weight is preferably 90000 or less.

  In addition, the said hydrosilyl group containing polyorganosiloxane compound may be used individually by 1 type, and may use 2 or more types by arbitrary combinations and a ratio.

[1-2-1-2] Polyorganosiloxane Compound Containing Silanol Group As a preferable example of the polyorganosiloxane compound (b) contained in the liquid composition (B) according to the present invention, a polyorganosiloxane containing a silanol group The siloxane compound (hereinafter sometimes referred to as “polyorganosiloxane compound (b2)”) will be described in detail. Since the polyorganosiloxane compound has a silanol group in the siloxane skeleton, it reacts with the polyorganosiloxane compound (a) containing the silanol group contained in the liquid composition (A) to behave as a reactive solvent. In addition, the crosslinking density can be easily adjusted.
Silanol groups generally have a high reaction activity, and since the liquid composition (B) contains a condensation catalyst, the polyorganosiloxane compound (b2) contained therein is stored during storage of the liquid composition (B). In order to suppress the generation of water droplets due to the thickening of the water and condensation of silanol groups, those having moderately low reactivity are preferable.
Specifically, the polyorganosiloxane compound (b2) is preferably a linear polyorganosiloxane containing two silanol groups in one molecule.
The weight average molecular weight of the polyorganosiloxane compound (b2) is usually 1000 to 20000, preferably 1500 to 10,000. When the weight average molecular weight of the polyorganosiloxane compound (b2) is smaller than this range, the reaction activity is too high, and during storage, the polyorganosiloxane compound (b2) reacts with the coexisting condensation catalyst and the liquid composition (B) May cause significant thickening or a large amount of water droplets. When the weight average molecular weight is larger than this range, the reaction activity is too low, and the polyorganosiloxane compound (b) is obtained from a cured product obtained by mixing the liquid composition (A) and the liquid composition (B). May bleed out.

[1-2-1-3] Polyorganosiloxane compound containing an organic group containing a hydroxyl group As a preferred example of the polyorganosiloxane compound (b) contained in the liquid composition (B) according to the present invention, an organic compound containing a hydroxyl group. The polyorganosiloxane compound containing a group (hereinafter sometimes referred to as “polyorganosiloxane compound (b3)”) will be described in detail.
Since the polyorganosiloxane compound (b3) has an organic group containing a hydroxyl group in the siloxane skeleton, the crosslinking density can be easily adjusted. It is preferable that two or more organic groups containing a hydroxyl group are contained in one molecule.

  A siloxane compound containing two or more organic groups containing a hydroxyl group in one molecule is at least two Si—R—OH bonds formed in the molecule between Si in the siloxane skeleton and an organic group containing a hydroxyl group. Preferably, it is a linear, branched, or three-dimensional net-like polyorganosiloxane compound having three or more.

  Note that R in the Si—R—OH bond represents a divalent substituent having 1 or more carbon atoms. The number of carbon atoms in R is preferably 2 or more, usually 25 or less, preferably 20 or less, and further 10 or less. Further, when it has 2 or more carbon atoms, it may have one or more multivalent atoms or atomic groups selected from an ether bond, an ester bond, an amide bond, a urethane bond and the like. R preferably has no aliphatic unsaturated bond from the viewpoint of heat resistance and light resistance.

Moreover, as the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom other than the organic group containing the hydroxyl group, the above-mentioned hydrosilyl group-containing polyorganosiloxane compound (organohydrogenpolysiloxane) in the “silicon atom” The same as “bonded substituted or unsubstituted monovalent hydrocarbon group”.
Examples of the organosilane and polyorganosiloxane include carbinol-modified polydimethylsiloxane and polyol-modified polydimethylsiloxane having an alcoholic hydroxyl group at the side chain or terminal.

  Among these, compounds (3a) to (3d) represented by the following general formula can be preferably used. Commercially available products can also be used. For example, X-22-4039, X-22-4015, X-22-160AS, KF-6001, KF-6002, KF-6003, X manufactured by Shin-Etsu Chemical Co., Ltd. -22-176DX, X-22-176F, XF42-B0970 manufactured by Momentive Performance Materials Japan GK, IM11 manufactured by Asahi Kasei Wacker Silicone, IM16, IM22, BY16-201 manufactured by Toray Dow Corning Silicone Can do.

(In general formulas (3a) to (3d), m and n represent an integer of 1 or more.)

[1-2-2] Condensation catalyst (curing catalyst)
The liquid composition (B) according to the present invention contains a condensation catalyst, that is, a dehydration / dealcohol condensation reaction catalyst, a dehydrogen condensation reaction catalyst, particularly a siloxane compound dehydration / dealcohol condensation reaction catalyst, and a dehydrogen condensation reaction catalyst.

  The dehydration / dealcohol condensation reaction catalyst preferably contains at least one selected from the group consisting of an organometallic complex catalyst, a salt of a metal and an organic acid, and a Lewis acid / Lewis base catalyst.

  As the metal component contained in the dehydration / dealcohol condensation reaction catalyst, it is preferable to use one or more selected from Sn, Zn, Fe, Ti, Zr, Bi, Hf, Y, Al, B, Ga, etc. , Ti, Al, Zn, Zr, Hf, and Ga are preferable in that they have high reaction activity. When used as a light emitting device member, they have moderate catalytic activity with little electrode corrosion and light absorption. Zr, Hf, and Ga are particularly preferable because unnecessary cutting deterioration hardly occurs.

The siloxane compound dehydrogenative condensation catalyst preferably contains at least one selected from the group consisting of metals, boron and hydroxylamine.
The metal components contained in the dehydrogenative condensation reaction catalyst include Pt, Pd, Pb, Sn, Zn, F
It is preferable to use one or more selected from e, Ti, Zr, Bi, and Al. Among them, Zr, Pt, Pd, and Sn are preferable in that they have a high reaction activity, have an appropriate activity, and can easily control the reaction rate. Zr and Sn which are easily available industrially are more preferable. Among the condensation catalysts containing Sn (Sn-based catalyst), Sn (IV) -based is more preferable. Further, when the cured product is used near the electrode, it is preferable to use a Zr-based catalyst, hydroxylamine, platinum-based catalyst, or the like, which hardly causes electrode coloring.

  When the hydrosilyl group-containing polyorganosiloxane compound (polyorganosiloxane compound (b1)) is included in the liquid composition (B), the liquid composition (B) is mixed with the liquid composition (A) and the liquid composition (B). ), The dehydration / dealcoholization condensation reaction of the polyorganosiloxane compound (a) containing the silanol group contained in the liquid composition (A) itself, the polyorganosiloxane compound (a) and the polyorganosiloxane compound (A). The dehydrogenative condensation reaction with the organosiloxane compound (b1) may proceed simultaneously. In such a case, a catalyst having activity for both dehydration / dealcohol condensation reaction and dehydrogenation condensation reaction can be used. Examples of such a catalyst include organometallic complex catalysts containing Zr, Hf, Sn, Zn, Fe, Ti, Al, B and the like, salts of these metals and organic acids, and the like. Above all, even when it remains in the cured product, there is little electrode corrosion, less light absorption, a balance of activities of dehydration / dealcoholization condensation and dehydrogenation condensation, moderate activity and easy reaction control. To Zr and Hf-containing catalysts are preferred.

Specific examples of the organometallic compound catalyst containing zirconium include zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetranormal propoxide, zirconium tetraisopropoxide, zirconium tetra Examples thereof include normal butoxide, zirconium acylate, zirconium tributoxy systemate, zirconium octoate, zirconyl (2-ethylhexanoate), and zirconium (2-ethylhexoate).
As the organometallic compound catalyst containing zirconium, for example, various zirconium catalysts described in JP 2010-163602 A can be used in addition to the above compounds.
In particular, for use in the liquid composition (B) of the two-component composition of the present invention, it is important that the catalyst itself has appropriate stability and catalytic reactivity. It is preferably not hydrolyzed.
Examples of such ligands that give moderate stability and catalytic reactivity include monocarboxylic acids such as stearic acid, naphthenic acid, and octylic acid, and dicarboxylic acids such as acetylacetone. It is preferable that at least one of them is a salt bonded to these carboxylic acids. Further, the zirconium catalyst may have a zirconyl structure (Zr = O2 +).
Moreover, even if a zirconium catalyst is contained, the liquid composition (B) is transparent, has no precipitate during long-term storage of about 6 months, and has a curing performance when the liquid compositions (A) and (B) are mixed. If maintained, the zirconium catalyst may be in the form of a powder or an oligomer, and the liquid composition (B) is a polyorganosiloxane compound containing a silanol group (polyorganosiloxane compound (b2)). ) May be bonded to or coordinated with the silanol group of the polyorganosiloxane compound.
If the storage stability of the liquid composition (B) is satisfied, a part of the four valences of zirconium in the zirconium catalyst may be bonded to an alkoxy group. In the case of a catalyst supplied in a form dissolved in an alcohol serving as a ligand, such as zirconium tetra-n-propoxide, the alcohol introduced into the system together with the catalyst is a liquid composition (A) or a liquid composition ( It is preferable to use it in a form that eliminates unnecessary alcohol as much as possible because it tends to cause curing failure because it produces an alkoxy group having poor reactivity by transesterification with the silanol group of the silanol group-containing polyorganosiloxane compound of B). Moreover, in order to supplement the storage stability and catalyst solubility of the liquid composition (B), a solvent that coordinates to the catalyst, such as acetylacetone, may be added as appropriate to the liquid composition (B).
As described above, the zirconium catalyst has been described, but the same can be said for other metal catalysts.

Hereinafter, specific examples of the condensation catalyst other than the organometallic compound catalyst containing zirconium will be described.
Examples of the organometallic compound catalyst containing hafnium include the same form as the zirconium.
Examples of the titanium-containing organometallic compound catalyst include titanium tetraisopropoxide, titanium tetranormal butoxide, butyl titanate dimer, tetraoctyl titanate, titanium acetylacetonate, titanium octylene glycolate, and titanium ethyl acetoacetate.

Examples of the organometallic compound catalyst containing zinc include zinc triacetylacetonate, zinc stearate, zinc octylate, bis (acetylacetonato) zinc (II) (monohydrate), and the like.
As the organometallic compound catalyst containing tin, tetrabutyltin, monobutyltin trichloride, dibutyltin dichloride, dibutyltin oxide, tetraoctyltin, dioctyltin dichloride, dioctyltin oxide, tetramethyltin, dibutyltin laurate, dioctyltin laurate, Bis (2-ethylhexanoate) tin, bis (neodecanoate) tin, di-n-butylbis (ethylhexylmalate) tin, di-normalbutyl bis (2,4-pentanedionate) tin, di-normalbutylbutoxy Examples include chlorotin, di-normal butyl diacetoxy tin, di-normal butyl dilaurate tin, and dimethyl dineodecanoate tin.

Examples of the boron-containing catalyst include trimethoxyborane, triethoxyborane, tributoxyborane, and tris (pentafluorophenyl) borane.
Examples of the gallium-containing catalyst include gallium triacetylacetonate, gallium triethoxide, diethylethoxygallium, gallium octylate, gallium laurate, and the like.
Platinum vinyl siloxane complex, chloroplatinic acid, etc. can also be suitably used. However, since the cured product tends to be a foam, it can be used in combination with a curing inhibitor such as ethynylcyclohexanol as necessary. When step temperature rise is set, foaming can be suppressed.

As the condensation catalyst not containing a metal, a base catalyst or an organic acid catalyst that volatilizes after curing, such as diethylhydroxylamine and triethylamine, may be used.
The said condensation catalyst may be used individually by 1 type, and may be used 2 or more types by arbitrary combinations and a ratio. Moreover, you may use together with arbitrary reaction promoters and reaction inhibitors.
Further, after mixing the liquid compositions (A) and (B), the condensation reaction mechanism caused by the condensation catalyst may be only a dehydration / dealcoholization condensation reaction or only a dehydrogenation condensation reaction, and both reactions coexist. However, in order to reduce the risk of foaming at the time of curing, it is preferable that the dehydration / dealcohol condensation reaction is a main component because the reaction rate can be easily controlled.

It is important that the condensation catalyst is mixed with the liquid compositions (A) and (B) and then added in such an amount that the two-component composition of the present invention is at least cured and does not foam significantly during curing. . The content of the condensation catalyst is, for example, 0.001% by weight or more, preferably 0.005% by weight or more, based on the total raw material weight excluding the volatile organic solvent, in terms of hydroxylamine, boron or metal element. More preferably, it is 0.01% by weight or more, usually 5% by weight or less, preferably 1% by weight or less, more preferably 0.3% by weight or less.
The content of the condensation catalyst can be measured by ICP analysis.

  In particular, in the case of using a metal alkoxide catalyst or Sn (IV) catalyst, the content of the condensation catalyst is selected from a volatile organic solvent from the viewpoint of suppressing the formation of metal oxides and insoluble catalyst substance oligomers that occur over time. It is preferable that it is 0.08 weight% or less in conversion of a metal element with respect to the removed total raw material weight.

[1-2-3] Pt content The liquid composition (B) according to the present invention is characterized by containing substantially no Pt.
Pt is dehydrogenated with the silanol group-containing polyorganosiloxane of the liquid composition (A) when the liquid composition (B) contains a polyorganosiloxane compound containing a hydrosilyl group (polyorganosiloxane compound (b1)). There is a catalytic action that causes a condensation reaction.
Since Pt has a very strong activity as a dehydrogenative condensation reaction catalyst, if the Pt content is too large, the liquid composition (A) and the liquid composition (B) are mixed and foamed by hydrogen when obtaining a cured product. Prone to occur. When the liquid composition (B) contains a polyorganosiloxane compound containing a hydrosilyl group, the hydrosilyl group of the polyorganosiloxane compound reacts with moisture in the atmosphere during long-term storage of the liquid composition (B). Then, hydrogen is generated and the silanol group is changed to a highly active silanol group, which tends to increase the viscosity of the liquid composition (B) with time.
Further, when a cured product obtained by curing the two-component composition of the present invention is used in the vicinity of a chip as a light emitting device member, if Pt remains in the cured product, the remaining Pt is caused by the heat or light of the chip. May form particles and absorb light.

From this point of view, “substantially not containing Pt” means that the liquid composition (B) does not contain “effectively common technical knowledge” to the extent that the liquid composition (B) impairs storage stability. Means. Specifically, the Pt content relative to the total weight of the liquid composition (B) is usually 1 ppm or less, preferably 0.5 ppm or less, in terms of metal weight.
For the same reason, even when Pt derived from the synthesis of the polyorganosiloxane compound (b) contained in the liquid composition (B) is unintentionally mixed, the Pt content needs to be 1 ppm or less.

[1-3] Other Additives The two-component composition of the present invention may be used alone. Other additives may be contained for the purpose of adjusting properties and improving optical properties, workability, mechanical properties, and physicochemical properties of the cured product (polyorganosiloxane cured product).
Among other additives, it is preferable to contain inorganic particles, a silicone-based crosslinking agent, and a liquid medium described below.

[1-3-1] Inorganic particles (filler)
The two-component composition of the present invention improves the optical properties, workability, mechanical properties, and physicochemical properties of the cured product (polyorganosiloxane cured product), and the following <1> to <5> For the purpose of obtaining any one of the effects 5>, at least one of the liquid compositions (A) and (B) may further contain inorganic particles.

  <1> By mixing inorganic particles as a light-scattering substance in the cured polyorganosiloxane and scattering the light generated from the semiconductor light-emitting element, the light amount of the semiconductor light-emitting element that hits the phosphor is increased and the wavelength conversion efficiency is improved. At the same time, the directivity angle of light emitted from the semiconductor light emitting device to the outside is expanded. Further, by mixing white inorganic particles as a light scattering material and functioning as a reflecting material, the light emitted from the semiconductor light emitting device is efficiently reflected to the outside of the device.

<2> Generation of cracks is prevented by blending inorganic particles as a binder with the cured polyorganosiloxane.
<3> The viscosity of the liquid composition (A) or (B) is increased by blending inorganic particles as a viscosity modifier.
<4> By adding inorganic particles to the cured polyorganosiloxane, the shrinkage is reduced and the adhesion is improved.
<5> By blending inorganic particles with the cured polyorganosiloxane, the refractive index is adjusted to improve the light extraction efficiency.
In such a case, an appropriate amount of inorganic particles may be mixed in the liquid composition (A) or (B) according to the purpose, as in the case of the phosphor powder. In this case, the effect obtained depends on the type and amount of the inorganic particles to be mixed.

For example, when the inorganic particles are ultrafine silica particles having a particle diameter of about 10 nm (Nippon Aerosil Co., Ltd., trade names: AEROSIL # 200 and RX200, Tokuyama Co., Ltd., trade names: Leoroseal QS-102 and HM-20L), Since the thixotropic property of the liquid composition (A) and / or the liquid composition (B) is increased, the effect <3> is great.
Further, when the inorganic particles are crushed silica or spherical silica having a particle size of about several μm, there is almost no increase in thixotropic property, and the function of the cured polyorganosiloxane as an aggregate is the center. And the effect of <4> is large.

In addition, when inorganic particles such as titania or alumina having a particle size of about 1 μm, which have a refractive index different from that of the cured polyorganosiloxane, light scattering at the interface between the cured polyorganosiloxane and the inorganic particles increases, The effect of 1> is great.
In addition, when using inorganic particles having a particle size of 3 to 5 nm larger than that of the cured polyorganosiloxane, specifically, a particle size equal to or smaller than the emission wavelength, the refractive index is maintained while maintaining the transparency of the cured polyorganosiloxane. The above effect <5> is great.

  Accordingly, the type of inorganic particles to be mixed may be selected according to the purpose. Moreover, the kind may be single and may combine multiple types. Moreover, in order to improve dispersibility, it may be surface-treated with a surface treatment agent such as a silane coupling agent.

[1-3-1-1] Types of inorganic particles The types of inorganic particles used are inorganic oxides such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, and yttrium oxide. Examples include nitrides such as particles, silicon nitride, boron nitride, silicon carbide, and aluminum nitride, carbon compounds, diamond particles, etc., but other substances can be selected according to the purpose, and are limited to these. is not.

  The form of the inorganic particles may be any form depending on the purpose, such as powder form, slurry form, etc., but when it is necessary to maintain transparency, the polyorganosiloxane cured product of the present invention has the same refractive index, It is preferable to add it as a solvent-based transparent sol to the liquid composition (A) and / or the liquid composition (B).

[1-3-1-2] Average particle diameter (median diameter) of inorganic particles
The average particle diameter of these inorganic particles (primary particles) is not particularly limited, but is usually about 1/10 or less of the phosphor particles. Specifically, those having the following average particle diameter are used according to the purpose. For example, if inorganic particles are used as the light scattering material, the average particle size is preferably 0.1 to 10 μm. For example, if inorganic particles are used as the aggregate, the average particle size is preferably 1 to 100 μm. For example, if inorganic particles are used as a thickener (thixotropic agent), the average particle size is preferably 5 to 100 nm. Moreover, for example, if inorganic particles are used as the refractive index adjuster, the average particle size is preferably 1 to 10 nm.

[1-3-1-3] Inorganic particle mixing method
In the present invention, the method for mixing the inorganic particles is not particularly limited, but usually it is recommended to mix while defoaming using a planetary stirring mixer or the like. For example, when mixing small particles such as Aerosil that are prone to aggregation, the aggregated particles are crushed using a bead mill, three rolls, high shear stirrer, etc. You may mix the large particle component which is easy to mix.

[1-3-1-4] Content of inorganic particles The content of inorganic particles in the cured polyorganosiloxane of the present invention is arbitrary as long as the effect of the present invention is not significantly impaired, and is selected according to the application form. That's fine. For example, when inorganic particles are used as the light scattering agent in the sealant, the content is preferably 0.01 to 10% by weight with respect to the total weight of the liquid compositions (A) and (B). Moreover, when using the hardened | cured material which contained the light-scattering agent in high concentration as a reflective material of a light-emitting device or a frame material which has a reflective function and surrounds a chip | tip, the content is liquid composition (A) and 5 to 80% by weight with respect to the total weight of (B), and 10 to 70% by weight with good coating and molding processability are preferred. For example, when inorganic particles are used as the aggregate, the content is preferably 1 to 50% by weight with respect to the total weight of the liquid compositions (A) and (B). For example, when using inorganic particles as a thickener (thixotropic agent), the content is preferably 0.1 to 20% by weight with respect to the total weight of the liquid compositions (A) and (B). . For example, when using inorganic particles as a refractive index adjuster, the content is preferably 10 to 80% by weight based on the total weight of the liquid compositions (A) and (B).
If the amount of the inorganic particles is too small, the desired effect may not be obtained. If the amount is too large, various properties such as adhesion, transparency, moldability, and hardness of the cured product may be adversely affected. From the viewpoint of uniformly mixing the inorganic particles into the liquid compositions (A) and (B), the inorganic particles are preferably contained in the liquid composition (A) more than the liquid composition (B). Usually, it is preferable to adjust the content of the inorganic particles so that the viscosity of the liquid composition (B) does not exceed the viscosity of the liquid composition (A). More preferably, the total amount of the inorganic particles is contained in the liquid composition (A).

  The two-part composition of the present invention has a lower viscosity than conventional optical member materials such as epoxy resins and silicone resins, and is well-suited to phosphors and inorganic particles, and disperses high-concentration inorganic particles. However, there is an advantage that the coating performance can be sufficiently maintained. In addition, it is possible to increase the viscosity by adjusting the degree of polymerization and adding a thixotropic agent such as aerosil as necessary, and the adjustment range of the viscosity according to the target inorganic particle content is large. It is possible to provide a coating solution that can flexibly cope with various coating methods such as potting, spin coating and printing.

In addition, the content and concentration distribution of the inorganic particles in the polyorganosiloxane cured product can be calculated from the charged composition, and the cured product is chemically dissolved to perform ICP analysis of elements peculiar to the inorganic particles, or to create a cross section of the cured product It can be obtained by performing image processing after taking a picture.
Moreover, what is necessary is just to set the content of the inorganic particle in the two-component composition of the present invention so that the content of the inorganic particle in the cured polyorganosiloxane falls within the above range. Therefore, when the two-component composition does not change in weight in the drying step, the content of inorganic particles in the two-component composition is the same as the content of inorganic particles in the cured polyorganosiloxane. In addition, when the two-component composition changes in weight in the drying step, such as when the two-component composition contains a solvent or the like, the content of inorganic particles in the two-component composition excluding the solvent or the like May be the same as the content of inorganic particles in the cured polyorganosiloxane.

[1-3-1-5] Combined Use of Conductive Filler and Thermally Conductive Filler Further, when an optical member comprising at least the cured polyorganosiloxane of the present invention is used in a semiconductor light emitting device For example, a conductive filler may be included for the purpose of forming an electric circuit, or a heat conductive filler may be included for the purpose of providing a die bond layer. Thereby, electroconductivity and heat conductivity can be provided to polyorganosiloxane hardened | cured material.

  The types of filler used include plating with noble metal powders such as silver powder, gold powder, platinum powder and palladium powder, noble metal powders such as copper powder, nickel powder, aluminum powder, brass powder and stainless steel, and noble metals such as silver, Examples include alloyed base metal powder, organic resin powder and silica powder coated with precious metal or base metal, carbon filler such as carbon black and graphite powder, ceramic powder such as SiC, SiN, AlN, BN, diamond powder, etc. However, other substances can be selected according to the purpose, and the present invention is not limited to these. In addition, the conductive filler may be used alone or in combination of two or more in any combination and ratio.

[1-3-2] Silicone-based crosslinking accelerator In the two-component curable polyorganosiloxane composition of the present invention, in addition to controlling the catalyst concentration and the amount used, a highly reactive silicone-based crosslinking accelerator is used as a crosslinking accelerator component. As a result, the curing rate can be increased.
The silicone-based crosslinking accelerator in the present invention means at least 2 silanol groups and / or hydrolyzable silyl groups that react with silanol groups of the polyorganosiloxane compound (a) in the liquid composition (A) in one molecule. It is a polyfunctional silicon-containing polyorganosiloxane compound containing at least one.
The silicone-based crosslinking agent has a higher reactivity than the polyorganosiloxane compound (a) in the liquid composition (A), and has two or more groups that react with the silanol group, whereby in the liquid composition (A). It functions as a strong binder for bonding the polyorganosiloxane compounds (a) to each other and promotes curing.
This silicone cross-linking accelerator is added to at least one of the liquid compositions (A) and (B) before mixing the liquid compositions (A) and (B), so that the polyorgano in the liquid composition (A) is added. By converting the silanol group of the siloxane compound (a) to a terminal having a higher reaction activity, the curing rate can be increased when mixing the liquid compositions (A) and (B).

The main skeleton of the silicone-based crosslinking accelerator is preferably a polyorganosiloxane structure mainly composed of trifunctional (T unit) and / or tetrafunctional (Q unit) silicon, and is a non-reactive organic substance bonded to silicon. The functional group is usually a methyl group or a phenyl group from the viewpoint of excellent heat resistance and light resistance, and preferably a methyl group capable of providing a silicone-based cross-linking accelerator that has no ultraviolet absorption, lower electron emission than the phenyl group, and higher reactivity. It is preferable that the group is mainly used.
Since the silanol group derived from trifunctional or higher silicon is more active in the electronic environment than the silanol group derived from bifunctional silicon, the reactivity is increased.
The reactivity of the silanol group is also affected by the molecular weight of the polyorganosiloxane that is the trunk molecule, and the lower the molecular weight, the less the steric hindrance and the higher the activity. Therefore, in order to increase the curing speed, the lower the molecular weight of the silicone-based cross-linking accelerator, the better, but if the molecular weight is too low, the boiling point will be low, and volatilization during curing will not give a sufficient effect, Even if it does not volatilize, the reactivity is too high and the surface of the cured product may be roughened.

  The molecular weight of the silicone-based crosslinking accelerator is appropriately selected depending on its use, the shape of the member used, and the processing method. The weight average molecular weight is usually 200 or more, preferably 250 or more, more preferably 300 or more, and the upper limit is usually 100,000 or less, preferably Is 5000 or less, more preferably 1000 or less.

The curing rate can also be controlled by the amount of silicone crosslinking accelerator used. A suitable amount depends on the molecular weight of the silicone-based crosslinking accelerator, but is usually 0.05 to 5 parts by weight, preferably 0.005 parts by weight based on 100 parts by weight of the polyorganosiloxane compound in the liquid composition (A). 1 to 3 parts by weight, more preferably 0.15 to 2 parts by weight, particularly preferably 0.2 to 1 part by weight.
Below this range, the effect as a crosslinking accelerator may not be sufficiently exhibited. Further, if the amount exceeds this range, the resulting cross-linking is too brittle, or the volatilization or condensation reaction of the polyorganosiloxane compound (a) in the liquid composition (A) and the unreacted silicone-based cross-linking accelerator is caused. Due to an increase in the amount of water, alcohol and the like to be released, the weight yield at the time of curing is reduced, or excessive internal stress is generated in the obtained cured product. As a result, deformation, wire breakage, member peeling, and the like may occur when a semiconductor light emitting device is formed, and the reliability of the device may be reduced.

The silicone-based crosslinking accelerator may be added to either the liquid composition (A) or (B), but from the viewpoint of the storage stability of the liquid obtained, the liquid composition (A) side does not contain a condensation catalyst. It is preferable to add.
By adding to the liquid composition (A) side, the liquid composition (A) has excellent storage stability at room temperature and is less likely to cause thickening and turbidity while maintaining the original properties of the liquid composition (B). During mixing, it can be cured in a short time.
The reactive terminal of the silicone-based crosslinking accelerator may be a silanol group or a hydrolyzable silyl group. The hydrolyzable silyl group is preferably an alkoxy group or a ketoxime group from the viewpoint that the component to be removed after hydrolysis is neutral. Among them, an alkoxy group having 1 to 3 carbon atoms is preferable from the viewpoint of reactivity and availability. Particularly preferred is a methoxy group having a low reactivity and a small molecular weight of the component to be eliminated.

  On the other hand, when added to the liquid composition (B) side, since a high concentration condensation catalyst coexists, the reactive end of the silicone-based crosslinking accelerator is not a silanol group but hydrolyzed to suppress the reactivity. It is preferably a functional silyl group. Preferred hydrolyzable silyl groups are the same as those added to (A). The liquid composition (B) after the addition of the silicone-based crosslinking accelerator is sealed in order to prevent the hydrolysis of the silicone-based crosslinking accelerator from being accelerated by moisture in the air and proceeding to increase the viscosity of the liquid composition (B). It is preferable to avoid contamination with moisture.

[1-3-3] Liquid medium The two-component composition of the present invention is used for the purpose of adjusting properties such as viscosity, curing speed, hardness of the cured product, improved solubility of the catalyst, and ease of application. You may mix with another liquid medium.
As the other liquid medium, an organic solvent having no hydroxyl group or hydrosilyl group, silicone oil, or the like can be used.

  An appropriate amount of the liquid medium to be used is appropriately selected depending on the application form of the two-component composition of the present invention to a light emitting device. For example, when a phosphor and a thixotropic agent are mixed and dispersed in the two-component composition of the present invention, and a phosphor layer is applied in a thin layer on a large number of light emitting elements and light emitting devices by screen printing, In order to control the properties, 5 to 30% by weight, preferably 10 to 20% by weight of the coating solution may be used as the liquid medium.

[1-4] Method of Mixing Liquid Compositions (A) and (B) When the two-component composition of the present invention obtains a cured product as an optical member, the liquid compositions (A) and (B) Mix and cure. The amount of the liquid compositions (A) and (B) to be cured is such that Si-OH (silanol group) contained in the polyorganosiloxane compound of the liquid composition (A) and the liquid composition (B) are mixed. The molar ratio of the substituent that reacts with the silanol group contained in the polyorganosiloxane (for example, Si—H (hydrosilyl group)) is usually 100: 1 to 1: 100, preferably 20: 1 to 1:20, more preferably. Is 10: 1 to 1:10. Even if there are too many silanol group-containing polyorganosiloxane compounds contained in the liquid composition (A), or there are too many polyorganosiloxane compounds containing substituents that react with the silanol groups contained in the liquid composition (B). Curing may be insufficient.

  In addition, the substituent other than the substituent which reacts with the silanol group contained in the polyorganosiloxane compound of the liquid composition (A) and the silanol group contained in the polyorganosiloxane compound of the liquid composition (B), and the ratio thereof, It is preferable to set appropriately from the viewpoint of the stability of the curing reaction.

For example, the R ^{1 to} R ¹⁷ substituents of the polysiloxane compounds of the general formula (1) and the general formula (2) are 95 mol% or more, preferably 98 mol% or more, more preferably the substituents excluding the hydride group and the hydroxyl group. Preferably, 99 mol% or more is an alkyl group. The alkyl group is usually 100 mol% or less. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group, and a methyl group is preferable from the viewpoint of stability.

  That is, since the hydride group and the hydroxyl group are essential substituents for the curing reaction, the hydride group and the hydroxyl group need to be appropriately contained, but other substituents are alkyl groups from the viewpoint of light and thermal stability of the cured product. Those containing a large amount of are preferable. If too few alkyl groups are substituted with other functional groups, the stability becomes poor.

[1-5] Curability The two-component composition of the present invention is desired to be cured in air, usually at a temperature of 150 ° C. within 6 hours. That is, the two-component composition of the present invention is economically superior because it has a relatively short curing time, and has a technical significance that the filler does not settle when the filler is added, mixed, and kneaded. . In addition, since curing can be performed at a relatively low temperature of 150 ° C., it is possible to suppress deterioration in performance of components of the semiconductor light emitting device, particularly the semiconductor light emitting element and the phosphor, due to heat during curing.

Here, in the present invention, “curing” refers to changing from a state exhibiting fluidity to a state not exhibiting fluidity. For example, the object is allowed to stand for 30 minutes in a state inclined 45 degrees from the horizontal. Thus, the uncured state and the cured state can be determined depending on whether there is fluidity.
In a system in which a filler is added at a high concentration, there may be a case where the object is not cured even if it has no fluidity in a state where the object is tilted 45 degrees from the horizontal due to the expression of thixotropy. An uncured state and a cured state can be determined by measuring with a durometer type A and determining whether the hardness measurement value is at least 5 or more.
The time for curing the two-part composition of the present invention at a temperature of 150 ° C. is usually within 6 hours, more preferably within 5 hours, particularly preferably within 4 hours, and particularly preferably within 3 hours. Moreover, it is 0.2 hour or more normally, Preferably it is 0.5 hour or more. If the curing time is too long, the filler may settle in the case of a composition containing the filler. Further, since a long curing process is required, the cost is increased. If the curing time is too short, handling may be difficult, and the surface may be cured before leveling and unevenness may be formed.

In order to increase the curing speed, select an appropriate catalyst, use a polysiloxane raw material with many branches, use a polysiloxane raw material with a high molecular weight, and remove desorbing components such as hydrogen, moisture and alcohol generated during curing. There are methods such as aggressive removal.
Further, the two-component composition of the present invention is characterized in that the film thickness becomes relatively thin by curing. This has excellent technical significance in that foaming is small and a uniform film can be produced.

  That is, the two-component composition of the present invention has an average height (thickness) of usually 0.12 cm or less, preferably 0.118 cm or less, more preferably 0.115 cm or less in the following curing test. Usually, it is 0.09 cm or more, preferably 0.1 cm or more. The average height increases because it contains bubbles and air. If the average height is too high, foaming may occur. If it is too low, the solid content is low. In some cases, curing shrinkage may occur.

[Curing test]
(1) 2 g of the two-component composition of the present invention is allowed to stand at a temperature of 150 ° C. for 6 hours in a polytetrafluoroethylene container having a bottom diameter of 5 cm and a height of 1 cm.
(2) After the treatment of (1), it is confirmed that there is no fluidity (cured) even if the inside of the polytetrafluoroethylene container is tilted by 45 degrees for 30 minutes.
(3) The average value of the height from the inner bottom of the container to the upper surface of the cured product is measured.

In order to prevent the cured product from becoming a foam, the thickness in liquid (liquid height) and the thickness after curing (height) are not significantly different from each other, generated hydrogen, dissolved air, moisture, organic solvents It is advisable to control the curing rate so that curing occurs after the volatile component such as has sufficiently exited the two-component composition system. For example, when the liquid composition (B) contains the polyorganosiloxane compound (b) containing a substituent that reacts with the silanol group, the two-part composition of the present invention is a liquid composition (A). The mixing ratio (A) :( B) of the polyorganosiloxane compound (a) in the liquid composition and the polyorganosiloxane compound (b) in the liquid composition (B) is 1: 1 to 1000: 1, preferably 1. : 1 to 50: 1, more preferably 1: 1 to 20: 1.
The molar ratio of Si—OH (silanol group) contained in the polyorganosiloxane compound (a) and the substituent that reacts with the silanol group contained in the polyorganosiloxane compound (b) (for example, Si—H (hydrosilyl group)). The raw material may be selected so that (= reactive functional group / silanol group) is usually 0 to 2, preferably 0 to 1, and more preferably 0.1 to 1.
In addition, since the molecular weight of the raw material polyorganosiloxane affects the reaction activity, for example, the molecular weight of the silanol group-containing polyorganosiloxane of the liquid composition (A) is preferably in the range of 500 to 50,000. A suitable concentration of the catalyst varies depending on the type of the catalyst, but is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, and usually 5% by weight in the total raw material weight. Hereinafter, it is preferably 1% by weight or less, more preferably 0.3% by weight or less.

[1-5] Refractive Index In order to obtain a cured polyorganosiloxane having a target refractive index, the two-component composition of the present invention is obtained immediately after mixing the liquid compositions (A) and (B). The refractive index of light having a wavelength of 589 nm at a temperature of 20 ° C. of the two-component composition is usually 1.42 or less, preferably 1.419 or less, more preferably 1.418 or less, usually 1.35 or more, Preferably it is 1.40 or more. When applied to an optical member, the refractive index of a general light-emitting device is about 2.5 or less, but in the present invention, the one having a relatively low refractive index is selected from the viewpoint of the light stability of the resin. Is preferred. In addition, when the light emission wavelength of the light emitting element is blue and high luminance is required as a sealing resin, but the luminance life of the light emitting device is not important, the light resistance required for the semiconductor light emitting device member does not become a big problem. . In that case, a refractive index of 1.42 or more and 1.55 or less may be used depending on the application. In order to obtain such a refractive index, a phenyl group, high refractive index nanoparticles, or the like is introduced within a range that does not hinder the function of the application, and the refractive index is adjusted. If the refractive index exceeds this value, there is a possibility that the reactivity will be lowered and the moldability and mechanical properties may be deteriorated.

The preferred refractive index ranges for the liquid compositions (A) and (B) are the same as the preferred ranges for the refractive index immediately after mixing. Since the liquid compositions (A) and (B) are in the above refractive index ranges, the liquid compositions (A) and (B) have similar functional group compositions, and are excellent in compatibility and have a polymer structure obtained. It becomes uniform.
The two-part composition of the present invention comprises a hydroxyl group derived from a silanol group contained in the polyorganosiloxane compound of the liquid composition (A) and a liquid group among all substituents bonded to silicon atoms of the polyorganosiloxane compound contained. 80 mol% or more, preferably 95 mol of the substituent excluding the substituent that reacts with the silanol group contained in the polyorganosiloxane of the composition (B) (hereinafter sometimes referred to as “substituent contributing to curing reaction”). % Or more, more preferably 99 mol% or more is an alkyl group. The alkyl group is preferably a methyl group.

  Among all the substituents bonded to the silicon atom of the siloxane compound, the molar fraction of the substituents excluding the substituents contributing to the curing reaction is liquid H-nuclear magnetic resonance spectrum, solid H-nuclear magnetic resonance spectrum, solid Si- It can be calculated by using a nuclear magnetic resonance spectrum or a combination of these in a complementary manner. That is, from the measured spectrum, (total number of moles of non-reactive organic groups such as alkyl groups bonded to silicon atoms of siloxane compound) / (total number of moles of all substituents bonded to silicon atoms of siloxane compound) ) × 100, the mole percentage can be calculated.

The case where the liquid compositions (A) and (B) of the two-component composition of the present invention contain the compounds of the general formulas (1) and (2), respectively, will be described as an example. Among ^{1 to} R ¹⁷ , those in which 80 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, particularly preferably 99 mol% or more of the total amount of substituents excluding hydride groups and hydroxyl groups are alkyl groups are preferred. Moreover, if the refractive index is too large and exceeds the refractive index of the light emitting device, the light extraction efficiency may not be improved. When an aromatic group such as a phenyl group is frequently used to obtain a high refractive index, there is a possibility that coloring is inferior in light resistance and heat resistance as compared with the case where the refractive index is within the preferred range of the present invention. If the refractive index is too small, for example, the light extraction efficiency may not be improved as compared with existing members for semiconductor light emitting devices.

  The refractive index of the two-component composition of the present invention can be measured with a refractometer. Specifically, an Abbe refractometer (using sodium D line (589 nm)) can be used. Abbe refractometer cannot be used if it contains filler and is opaque, but the content of organic groups directly bonded to polyorganosiloxane silicon by combining H-NMR, Si-NMR, elemental analysis, etc. And the composition ratio (for example, the ratio of phenyl group to methyl group) can be estimated to estimate the refractive index of the two-component composition of the present invention which is a binder component. For example, in a polydiorganosiloxane in which the organic group bonded to silicon is a methyl group and a phenyl group, the refractive index when the phenyl group content in all organic groups bonded to silicon is 0% is about 1.403, 50 The refractive index at the time of% is about 1.545, and the refractive index in the composition therebetween has a linear relationship according to the phenyl group content.

  Examples of the method for setting the refractive index of the two-component composition of the present invention in the above range include appropriately selecting the type and blending amount of the polyorganosiloxane compound as described later. In particular, in any, preferably all of the polyorganosiloxane compounds (for example, compounds of the general formulas (1) and (2)), the refractive index of light having a wavelength of 589 nm at a temperature of 20 ° C. of the polyorganosiloxane compound is Usually, it is 1.42 or less, preferably 1.419 or less, more preferably 1.418 or less, and usually 1.35 or more, preferably 1.40 or more. If the refractive index is too large and exceeds the refractive index of the light emitting device, the light extraction efficiency may not be improved. When an aromatic group such as a phenyl group is frequently used to obtain a high refractive index, there is a possibility that coloring is inferior in light resistance and heat resistance as compared with the case where the refractive index is within the preferred range of the present invention. If the refractive index is too small, for example, the light extraction efficiency may not be improved as compared with existing members for semiconductor light emitting devices. The refractive index of the polyorganosiloxane compound can be measured in the same manner as the refractive index of the two-component composition of the present invention.

[1-6] Properties of two-component composition The viscosity of the two-component composition of the present invention is not limited, but the viscosity at a liquid temperature of 25 ° C immediately after mixing the liquid compositions (A) and (B) Is usually 20 mPa · s or more, preferably 100 mPa · s or more, more preferably 200 mPa · s or more, and usually 10,000 mPa · s or less, preferably 5000 mPa · s or less, more preferably 1000 mPa · s or less. The viscosity can be measured with an RV viscometer (for example, an RV viscometer “RVDV-II ⁺ Pro” manufactured by Brookfield).

  Each viscosity of liquid composition (A) and (B) should just become said viscosity after mixing. When the liquid composition (B) contains a large amount of an organic solvent that does not react with the liquid composition (A), it is preferably a low molecular weight solvent that volatilizes all after curing, and is usually 100 mPa · s or less, preferably It is preferably 50 mPa · s or less, more preferably 10 mPa · s or less. In this case, in order to reduce curing shrinkage, the amount used is preferably 10% by weight or less, preferably 7% by weight or less of the liquid mixture (A) and (B) mixed solution. The solvent content of the liquid composition (B) is not particularly limited as long as it behaves as a reactive solvent that reacts with the other component during curing.

[2] Cured polyorganosiloxane The cured polyorganosiloxane of the present invention is obtained by curing the two-part composition of the present invention. The characteristics will be described below.

[2-1] Refractive index The refractive index of the cured polyorganosiloxane of the present invention is such that the refractive index of light having a wavelength of 589 nm at a temperature of 20 ° C. of the cured polyorganosiloxane of the present invention is usually 1.55 or less. Preferably, it is 1.42 or less, more preferably 1.419 or less, particularly preferably 1.418 or less, usually 1.35 or more, preferably 1.40 or more. When applied to an optical member, the refractive index of a general light emitting device is about 2.5 or less. preferable. In addition, light stability such as light extraction efficiency from the chip, hardness of cured product, reduction of gas permeability, etc. when the light stability of the resin is not a big problem depending on the use of the member for the semiconductor light emitting device of the present invention and the application site in the device. When other physical properties are important, a cured product having a high refractive index can be obtained by introducing a phenyl group or a high refractive index inorganic oxide nanosol. In this case, the refractive index of the cured polyorganosiloxane of the present invention is usually from 1.46 to 1.57, preferably from 1.50 to 1.55. If the refractive index is too large and exceeds the refractive index of the light emitting device, the light extraction efficiency may not be improved. When an aromatic group such as a phenyl group is frequently used to obtain a high refractive index, there is a possibility that coloring is inferior in light resistance and heat resistance as compared with the case where the refractive index is within the preferred range of the present invention. Moreover, if the refractive index is too small, for example, the light extraction efficiency may not be improved as compared with existing members for semiconductor light emitting devices.

  The refractive index of the polyorganosiloxane cured product of the present invention can be usually measured with a refractometer. Specifically, for example, an Abbe refractometer (using sodium D line (589 nm)) can be used with a single surface / independently cured film having a smooth surface molded to a film pressure of 1 mm or more as a sample. Abbe's refractometer cannot be used if it is opaque and contains a filler, but organic groups directly bonded to polyorganosiloxane silicon by combining solid H-NMR, solid Si-NMR, elemental analysis, etc. The refractive index of the two-component polyorganosiloxane cured product of the present invention, which is a binder component, can be estimated by examining the content and the composition ratio (for example, the ratio of phenyl groups to methyl groups). For example, in a polydiorganosiloxane in which the organic group bonded to silicon is a methyl group and a phenyl group, the refractive index when the phenyl group content in all organic groups bonded to silicon is 0% is about 1.403, 50 The refractive index at the time of% is about 1.545, and the refractive index in the composition therebetween has a linear relationship according to the phenyl group content.

[2-2] Transmittance
The polyorganosiloxane cured product of the present invention has a light transmittance of 80% or more, preferably 90% or more, more preferably 95% or more, at all wavelengths of 400 nm to 800 nm when the film thickness is 1 mm. .

[2-3] Other physical properties The polyorganosiloxane cured product of the present invention is mainly characterized by the above properties, but preferably has the following structure and properties.

[2-3-1] Basic skeleton The basic skeleton of the cured polyorganosiloxane of the present invention is usually a metalloxane skeleton, preferably the same inorganic siloxane skeleton (siloxane bond) as glass (silicate glass). Is preferred. The siloxane bond has the following excellent characteristics when the polyorganosiloxane cured product is used for an optical member.
(I) Light resistance is good because the bond energy is large and thermal decomposition and photolysis are difficult.
(II) It is slightly polarized electrically.
(III) The degree of freedom of the chain structure is large, a structure with high flexibility is possible, and the chain structure can freely rotate around the center of the siloxane chain.
(IV) The degree of oxidation is large and no further oxidation occurs.
(V) Rich in electrical insulation.

The silicon content of the cured polyorganosiloxane of the present invention is usually 20% by weight or more, preferably 25% by weight or more, and more preferably 30% by weight or more. On the other hand, as an upper limit, the silicon content of the glass composed only of SiO ₂ is 47% by weight, and therefore is 47% by weight or less. However, when making polyorganosiloxane hardened | cured material into a high refractive index, in order to contain the component required for high refractive index, it is 10 weight% or more normally, and is 47 weight% or less.

The silicon content of the cured polyorganosiloxane is analyzed by, for example, inductively coupled plasma spectroscopy (hereinafter abbreviated as “ICP” where appropriate) using the following method, and based on the results. Can be calculated.
[Measurement of silicon content]
The polyorganosiloxane cured product is pulverized to about 100 μm and baked in a platinum crucible in the air at 450 ° C. for 1 hour, then 750 ° C. for 1 hour, and 950 ° C. for 1.5 hours to remove carbon components. After that, add 10 times or more amount of sodium carbonate to a small amount of the obtained residue, heat with a burner to melt, cool it, add demineralized water, and adjust the pH to neutral with hydrochloric acid as silicon. The volume is adjusted to about several ppm and ICP analysis is performed.

[2-3-2] UV transmittance When the cured polyorganosiloxane of the present invention is used for an optical member for a semiconductor light-emitting device, the light transmittance at the emission wavelength of the semiconductor light-emitting device with a film thickness of 1 mm is: It is usually 80% or more, preferably 85% or more, and more preferably 90% or more. The light extraction efficiency of the semiconductor light emitting device has been enhanced by various techniques, but this was used when the transparency of the translucent member for sealing the semiconductor light emitting element or holding the phosphor was low. Since the brightness of the semiconductor light emitting device is reduced, it tends to be difficult to obtain a high brightness semiconductor light emitting device product.

  Here, the “emission wavelength of the semiconductor light emitting device” is a value that varies depending on the type of the semiconductor light emitting device, but is generally 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm. It refers to the following range of wavelengths. When the light transmittance at a wavelength in this range is low, the cured polyorganosiloxane absorbs light, the light extraction efficiency decreases, and a high-luminance semiconductor light-emitting device cannot be obtained. Furthermore, the energy corresponding to the decrease in light extraction efficiency is changed to heat, which causes thermal deterioration of the semiconductor light emitting device, which is not preferable.

In the ultraviolet to blue region (wavelength 300 nm to 500 nm), the sealing member easily deteriorates. Therefore, the cured polyorganosiloxane of the present invention having excellent durability is applied to a semiconductor light emitting device having an emission wavelength in this region. If used, the effect is increased, which is preferable.
The light transmittance of the cured polyorganosiloxane can be measured with an ultraviolet spectrophotometer using, for example, a sample of a single cured film having a smooth surface formed to a thickness of 1 mm by the following method.

(Measurement of transmittance)
Using an ultraviolet spectrophotometer (UV-3100, manufactured by Shimadzu Corporation) using a single cured product film having a smooth surface with a thickness of about 1 mm that is not scattered by scratches or unevenness of the cured polyorganosiloxane, a wavelength of 200 nm to The transmittance is measured at 800 nm.
However, the shape of the semiconductor light emitting device is various, and the majority is used in a thick film state exceeding 0.1 mm. There are applications using thin films, such as when a layer having a thickness of several μm containing phosphor particles or fluorescent ions is provided, or when a highly refractive light extraction film is provided on the thin film directly above the LED chip. In such a case, it is preferable to show a transmittance of 80% or more at this film thickness. Even in such a thin film application form, the polyorganosiloxane cured product of the present invention exhibits excellent light resistance and heat resistance, has excellent sealing performance, and can be stably formed without cracks.

[2-3-3] Peak Area Ratio The polyorganosiloxane cured product of the present invention preferably satisfies the following conditions. That is, the cured polyorganosiloxane of the present invention has a ratio of (chemical shift—total peak area of 40 ppm or more and 0 ppm or less) / (chemical shift—total area of peaks less than 40 ppm) in the solid Si-nuclear magnetic resonance spectrum. (Hereinafter referred to as “the peak area ratio according to the present invention” as appropriate) is usually 3 or more, preferably 5 or more, more preferably 10 or more, and usually 200 or less, preferably 100 or less, more preferably 50 or less. It is preferable.

  The peak area ratio according to the present invention is in the above range because the polyorganosiloxane cured product of the present invention has more bifunctional silicon than trifunctional or higher functional silicon such as trifunctional silicon or tetrafunctional silicon. Represents. Thus, by having many bifunctional or less silicon, the polyorganosiloxane hardened | cured material of this invention can exhibit an elastomer form, and it becomes possible to relieve stress.

  However, the polyorganosiloxane cured product of the present invention may exhibit an elastomeric shape without satisfying the above-described conditions for the peak area ratio according to the present invention. For example, the case where the polyorganosiloxane cured product of the present invention is produced using a coupling agent such as a metal alkoxide as a crosslinking agent corresponds to this case. The method for exhibiting the elastomeric form of the cured polyorganosiloxane of the present invention is arbitrary, and is not limited to the above-described conditions for the peak area ratio according to the present invention.

[2-3-4] Functional group The polyorganosiloxane cured product of the present invention has a predetermined functional group (for example, hydroxyl group, oxygen in a metalloxane bond, etc.) present on the surface of a resin such as polyphthalamide, ceramic or metal. And a functional group capable of hydrogen bonding. A container for a semiconductor light-emitting device (a cup or the like to be described later, hereinafter referred to as “semiconductor light-emitting device container” as appropriate) is usually formed of ceramic or metal. Moreover, a hydroxyl group usually exists on the surface of ceramic or metal. Therefore, for the purpose of ensuring adhesion, the functional group may have a hydrogen bond with the hydroxyl group. However, as described above, in the two-component curable polyorganosiloxane composition of the present invention, of all the substituents bonded to the silicon atom of the siloxane compound contained, the substituents other than the substituents contributing to the curing reaction are excluded. It is preferable that 80 mol% or more, preferably 95 mol% or more, more preferably 99 mol% or more is an alkyl group. The alkyl group is preferably a methyl group.

  Examples of the functional group capable of hydrogen bonding with respect to the hydroxyl group that the polyorganosiloxane cured product of the present invention has include, for example, silanol group, alkoxy group, amino group, imino group, methacryl group, acrylic group, thiol group, Examples thereof include an epoxy group, an ether group, a carbonyl group, a carboxyl group, and a sulfonic acid group. Of these, a silanol group and an alkoxy group are preferable from the viewpoint of heat resistance. The functional group may be one type or two or more types.

In addition, as described above, whether the polyorganosiloxane cured product of the present invention has a functional group capable of hydrogen bonding to a hydroxyl group is determined by solid Si-NMR, solid ¹ H-NMR, infrared absorption. It can be confirmed by spectroscopic techniques such as spectrum (IR) and Raman spectrum.

[2-3-5] Heat resistance The cured polyorganosiloxane of the present invention is excellent in heat resistance. That is, even when left under a high temperature condition, the transmittance of light having a predetermined wavelength does not easily change. Specifically, the cured product of the polyorganosiloxane of the present invention has a maintenance ratio of transmittance of light of 400 nm before and after being left at 200 ° C. for 500 hours, usually 80% or more, preferably 90% or more, more preferably. Is 95% or more, and is usually 110% or less, preferably 105% or less, more preferably 100% or less.

  The variation ratio can be measured by the transmittance measurement using an ultraviolet / visible spectrophotometer in the same manner as the UV transmittance measuring method described in [2-3-2].

[2-3-6] Light resistance The cured polyorganosiloxane of the present invention is excellent in light resistance. In particular, even when UV (ultraviolet light) is irradiated, the transmittance with respect to light having a predetermined wavelength is difficult to change. Specifically, the cured product of the polyorganosiloxane of the present invention usually has a transmittance maintenance factor of 400 nm light before and after irradiation with light having a center wavelength of 380 nm and a radiation intensity of 0.4 kW / m ² for 72 hours. It is 80% or more, preferably 90% or more, more preferably 95% or more, and is usually 110% or less, preferably 105% or less, more preferably 100% or less.

  The variation ratio can be measured by the transmittance measurement using an ultraviolet / visible spectrophotometer in the same manner as the UV transmittance measuring method described in [2-3-2].

[2-3-7] Residual amount of catalyst The polyorganosiloxane cured product of the present invention is usually produced using a curing catalyst (condensation catalyst). Therefore, these catalysts usually remain in the cured polyorganosiloxane of the present invention. Specifically, in the cured polyorganosiloxane of the present invention, the above-mentioned curing catalyst is usually 0.001% by weight or more, preferably 0.01% by weight or more, more preferably 0.02% by weight in terms of metal element. % Or more, usually 0.3% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less.

  The content of the curing catalyst can be measured by ICP analysis.

[2-3-8] Low boiling point component The cured product of the polyorganosiloxane of the present invention has a small chromatogram integrated area of a heat generation gas in the range of 40 ° C to 210 ° C in TG-mass (pyrolysis MS chromatogram). It is preferable that

  TG-mass is for detecting a low boiling point component in a cured polyorganosiloxane by raising the temperature of the cured polyorganosiloxane, but when the integrated area of the chromatogram is large in the range of 40 ° C. to 210 ° C., , Solvents and low-boiling components such as 3- to 5-membered cyclic siloxanes are present in the components. In such a case, (i) there is a possibility that the low-boiling point component increases and bubbles are generated or bleed out in the process of using the cured product, resulting in low adhesion to the semiconductor light emitting device container; There is a possibility that bubbles may be generated or bleed out due to heat generation. Therefore, it is preferable that the cured polyorganosiloxane of the present invention has few such low-boiling components.

In the cured polyorganosiloxane of the present invention, examples of a method for keeping the amount of the low boiling point component detected by TG-mass low include the following methods.
(I) The polymerization curing reaction is sufficiently performed so that unreacted raw materials having a low molecular weight do not remain.
(Ii) The low-boiling components are efficiently removed in steps other than the reaction step such as a polymerization reaction. For example, removing low boiling point components in the raw material in advance corresponds to that. Specifically, for example, it is usually 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 150 ° C. or lower, preferably 130 ° C. or lower, more preferably 120 ° C. or lower, preferably 100 mmHg or lower, preferably 20 mmHg. The process of distilling off the low-boiling components at the following pressure is performed on each raw material component before polymerization.

[2-3-9] Hardness The cured polyorganosiloxane of the present invention is preferably an elastomeric member. In general, optical members such as semiconductor light emitting devices often use a plurality of members having different coefficients of thermal expansion. However, the cured polyorganosiloxane of the present invention exhibits an elastomeric shape, resulting in expansion and contraction of the members used for the optical members. Stress can be relaxed. Therefore, it is possible to provide a semiconductor device that is less likely to be peeled, cracked, disconnected, or the like during use and is excellent in reflow resistance and temperature cycle resistance.

  Specifically, the cured polyorganosiloxane has a durometer type A hardness measurement (Shore A) of usually 5 or more, preferably 7 or more, more preferably 10 or more, and usually 90 or less, preferably 80 or less. More preferably, it is 70 or less. By having a hardness measurement value in the above range, the optical member of the present invention is less prone to cracking and can provide the advantages of excellent reflow resistance and temperature cycle resistance.

  The hardness measurement value (Shore A) can be measured by the method described in JIS K6253. Specifically, the measurement can be performed using an A-type rubber hardness meter manufactured by Furusato Seiki Seisakusho.

[2-3-10] Combination with other members Although the polyorganosiloxane cured product of the present invention may be used alone as a sealing material, it is an organic phosphor, a phosphor easily deteriorated by oxygen or moisture, and semiconductor light emission. For applications that require more strict shielding from oxygen and moisture, such as when sealing devices, the polyorganosiloxane cured product of the present invention is used to hold phosphors, seal semiconductor light emitting devices, and extract light Further, airtight sealing with a highly airtight material such as a glass plate or an epoxy resin may be performed on the outside, or vacuum sealing may be performed. There is no limitation on the shape in this case, and the sealed body, coated material or coated surface of the cured polyorganosiloxane of the present invention is substantially protected from the outside by a highly airtight material such as metal, glass or highly airtight resin. It suffices if there is no circulation of oxygen or moisture.

  Moreover, since the polyorganosiloxane cured product of the present invention has good adhesion as described above, it can be used as an adhesive for semiconductor light emitting devices. Specifically, for example, when bonding a semiconductor element and a package, when bonding a semiconductor element and a submount, when bonding package components, when bonding a semiconductor light emitting device and an external optical member, etc. The polyorganosiloxane cured product of the present invention can be used by coating, printing, potting and the like. Since the polyorganosiloxane cured product of the present invention is particularly excellent in light resistance and heat resistance, when it is used as an adhesive for a high-power semiconductor light-emitting device that is exposed to high temperature or ultraviolet light for a long time, it has a long-term use and high reliability. A semiconductor light emitting device having the same can be provided.

  In addition, the cured polyorganosiloxane of the present invention can ensure sufficient adhesion by itself, but the adhesion to the surface directly contacting the cured polyorganosiloxane for the purpose of further ensuring adhesion. Surface treatment for improvement may be performed. As such surface treatment, for example, formation of an adhesion improving layer using a primer or a silane coupling agent, chemical surface treatment using a chemical such as acid or alkali, plasma irradiation, ion irradiation or electron beam irradiation is used. Examples thereof include physical surface treatment, roughening treatment such as sand blasting, etching and fine particle coating. Other surface treatments for improving adhesion include, for example, JP-A-5-25300, Nogamihiro Inagaki, “Surface Chemistry” Vol. No. 18 9, pp21-26, “Surface Chemistry” by Kazuo Kurosaki, Vol. 19 No. 2, pp 44-51 (1998), etc., and known surface treatment methods.

[2-3-11] Others The shape and dimensions of the cured polyorganosiloxane of the present invention are not limited and are arbitrary. For example, when a polyorganosiloxane cured product is used as a sealing material for filling a semiconductor light emitting device container, the shape and dimensions of the polyorganosiloxane cured product of the present invention are the shape of the semiconductor light emitting device container and It is determined according to the dimensions. In addition, when the polyorganosiloxane cured product is formed on the surface of any substrate, it is usually formed in a film shape, and its dimensions are arbitrarily set according to the application. Even when the polyorganosiloxane cured product of the present invention is used for a light guide plate or an aerospace industry member, the shape can be arbitrarily used in accordance with the application site.

  However, one advantage of the cured polyorganosiloxane of the present invention is that it can be formed into a thick film when formed into a film. Conventionally used optical members have been difficult to thicken due to internal stress and other cracks when thickened, but the cured polyorganosiloxane of the present invention is stable and stable. Can be thickened. Specifically, the cured polyorganosiloxane of the present invention is preferably formed with a thickness of usually 0.1 μm or more, preferably 10 μm or more, more preferably 100 μm or more. In addition, although there is no restriction | limiting in an upper limit, Usually, it is 10 mm or less, Preferably it is 5 mm or less, More preferably, it is 1 mm or less. Here, when the thickness of the film is not constant, the thickness of the film refers to the thickness of the maximum thickness portion of the film.

  Moreover, the cured polyorganosiloxane of the present invention can usually seal a semiconductor light emitting device without causing cracks or peeling for a longer period of time than before. Specifically, a semiconductor light-emitting device is sealed using the polyorganosiloxane cured product of the present invention, and a driving current of usually 20 mA or more, preferably 350 mA or more is passed through the semiconductor light-emitting device to a temperature of 85 ° C. relative humidity. When continuous lighting is performed at 85%, the luminance after 500 hours or more, preferably 1000 hours or more, more preferably 2000 hours or more does not decrease compared to the luminance immediately after lighting.

Depending on the application, the cured polyorganosiloxane may contain other components. For example, in the case where the polyorganosiloxane cured product of the present invention is used as a constituent member of a semiconductor light emitting device, a phosphor or inorganic particles may be included. This point will be described later together with the description of the application.
Moreover, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

[3] Manufacturing method of polyorganosiloxane cured product The two-component composition of the present invention is composed of the liquid compositions (A) and (B) and other additives as required. The polyorganosiloxane cured product of the present invention can be obtained, for example, by mixing and curing the two-component composition of the present invention. The liquid compositions (A) and (B) are mixed immediately before use, and the mixing method is not particularly limited. When the mixed composition is heat-cured, hydrolysis polycondensation reaction between the polyorganosiloxane compounds (a) in the liquid composition (A), the polyorganosiloxane compounds (a) in the liquid composition (A), and The dehydrogenative condensation reaction of the polyorganosiloxane compound (b) in the liquid composition (B) and the hydrolysis polycondensation reaction between the polyorganosiloxane compounds (b) in the liquid composition (B) proceed simultaneously. The resulting cured product has a cross-linked structure mainly composed of siloxane bonds, and thus has excellent heat and light resistance and oxidation resistance.

The method for producing the cured polyorganosiloxane of the present invention is not limited as long as it has a step of curing the two-component composition of the present invention. If the polycondensate contains a solvent, the solvent may be distilled off in advance before drying.
The polyorganosiloxane cured product of the present invention is usually obtained by curing in air at a temperature of 150 ° C. within 6 hours, but preferred curing conditions will be described in detail below for carrying out the present invention. .

When the curing treatment is carried out at normal pressure, it is usually 15 ° C. or higher, preferably 50 ° C. or higher, more preferably 100 ° C. or higher, and usually 300 ° C. or lower, preferably 200 ° C. or lower, more preferably 170 ° C. or lower. To do. It is also possible to cure at a high temperature by maintaining the liquid phase by applying pressure.
Although the curing time varies depending on the reaction temperature, it is usually 0.1 hours or longer, preferably 0.5 hours or longer, more preferably 0.8 hours or longer, and usually 100 hours or shorter, preferably 20 hours or shorter, more preferably 15 hours. It is carried out in the range of less than time.

  In the above curing conditions, when the time is too short or the temperature is too low, the strength of the cured product may be insufficient due to insufficient polymerization. When the time is too long or the temperature is too high, the molecular weight of the two-component composition after mixing becomes high, the curing is too early, the structure of the cured product becomes nonuniform, and cracks are likely to occur. Furthermore, it is inferior in economic efficiency from the viewpoint of energy consumption. Based on the above tendency, it is desirable to appropriately select conditions according to desired physical property values.

  When either one of the liquid compositions (A) and (B) contains a solvent, or when a solvent is used in the mixing step of the liquid compositions (A) and (B), the curing treatment is usually performed. It is preferable to distill off the solvent from the liquid compositions (A) and (B) or the mixture before or during the (mixing step) (solvent distilling step). The obtained liquid semi-polycondensate can be cured and used as it is. The solvent is preferably distilled off after mixing the liquid compositions (A) and (B). In this case, it is preferable that the solvent is almost distilled off immediately before the fluidity is lost due to gelation. As a method for such solvent distillation, for example, until the fluidity is lost due to gelation, the solvent is distilled off at a temperature lower than the curing temperature, and then the temperature is raised above the curing temperature to obtain a cured product. It is preferred to do so.

The method of distilling off the solvent is arbitrary as long as the effects of the present invention are not significantly impaired. However, the solvent should not be distilled off at a temperature equal to or higher than the decomposition start temperature of the polyorganosiloxane compound contained in the two-component composition of the present invention.
When a specific range of the temperature conditions when the solvent is distilled off is given, it is usually 60 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and usually 450 ° C. or lower, preferably 300 ° C. or lower. More preferably, it is 200 degrees C or less. If the lower limit of this range is not reached, the evaporation of the solvent may be insufficient, and if it exceeds the upper limit, the two-component composition of the present invention may be gelled. In order to carry out distillation in such a temperature range, the boiling point of the solvent can be selected according to the intended use within the range of usually 50 to 200 ° C, preferably 70 to 180 ° C, more preferably 90 to 150 ° C.

Further, the pressure condition when the solvent is distilled off is usually atmospheric pressure. Further, if necessary, the pressure is reduced so that the boiling point of the reaction solution when the solvent is distilled off does not reach the decomposition start temperature. The lower limit of the pressure is such that the main component of the curable polyorganosiloxane composition does not distill.
The evaporation of the solvent may be performed when the semiconductor light emitting device is used for mounting. For example, when used as a sealing material, after potting the mixed solution (A) and (B) containing a solvent in the package recess after mounting the light emitting element, the solvent first evaporates at a low temperature that does not lead to curing. Examples include a step cure method in which the solvent is volatilized, and then the temperature is raised to the curing temperature to become solvent-free (A) and (B) the mixed liquid is cured. In addition, although the usage-amount of a volatile solvent changes with application | coating and shaping | molding methods, in order to suppress the shrinkage | contraction after hardening as much as possible and to ensure the dimensional accuracy of hardened | cured material, it is preferable to set it as the minimum required amount.
When the polyorganosiloxane cured product of the present invention is used as a semiconductor light-emitting device and is heated together with the semiconductor light-emitting device, it is usually at a temperature not higher than the heat resistance temperature of the component of the semiconductor light-emitting device, preferably 200. It is preferable to cure at a temperature of 0 ° C. or lower. In addition, since the present invention can be cured at a relatively low temperature of about 150 ° C. or lower as described above, when the purpose is to stabilize the components of the semiconductor light emitting device, particularly the semiconductor light emitting element and the phosphor. It is preferable to cure at 150 ° C. or lower.

[3-5] Others After the polymerization step described above, the obtained polyorganosiloxane cured product may be subjected to various post-treatments as necessary. Examples of the post-treatment include surface treatment for improving adhesion to the mold part, production of an antireflection film, production of a fine uneven surface for improving light extraction efficiency, and the like.

[4] Optical member Although the use of the cured polyorganosiloxane of the present invention is not limited, it has various properties such as light transmittance (transparency), light resistance, heat resistance, hydrothermal resistance, UV resistance, and low foamability. Since it is high, it can be suitably used for various optical members. Specific examples of the use of the optical member containing the cured polyorganosiloxane of the present invention include a semiconductor light emitting device, a light guide plate, and a member for the space industry.

The optical member containing the cured polyorganosiloxane of the present invention may be used with its shape and transparency appropriately determined depending on the use of the optical member, or may be used in combination with other compounds such as phosphors and inorganic particles. When these other compounds are used in combination, for example, a method of mixing and using the two-component composition of the present invention can be mentioned.
For example, when the optical member of the present invention is used for a member (sealing material) for sealing a semiconductor light emitting element or the like of a semiconductor light emitting device, it is used for a specific application by using phosphor particles and inorganic particles in combination. Furthermore, it becomes possible to use it suitably.

  When the cured polyorganosiloxane of the present invention is used as an optical member, for example, a phosphor is dispersed in the liquid composition (A) and / or (B) in the two-component composition of the present invention, and a semiconductor described later. It can be used as a wavelength converting member by molding in a cup of a light emitting device or applying it in a thin layer on an appropriate transparent support. The coating method is not particularly limited, and various methods such as spray coating, screen printing, and die coating can be used. Moreover, fluorescent substance may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The content of the phosphor in the cured polyorganosiloxane of the present invention is arbitrary as long as the effects of the present invention are not significantly impaired, but can be freely selected depending on the application form. For example, a white light emitting semiconductor light emitting device used for applications such as white LEDs and white illumination, when phosphors are uniformly dispersed and potted by filling the entire recess of the package including the semiconductor light emitting elements, the phosphor The total amount is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and usually 35% by weight or less, preferably 30% by weight or less, more preferably 28% by weight or less. .

  In addition, a phosphor dispersed at a high concentration in the same application is distant from the light emitting surface of the semiconductor light emitting element of the semiconductor light emitting device (for example, a package opening surface in which a recess including the semiconductor light emitting element is filled with a transparent sealing material, In the case of applying a thin film to a glass lid for LED hermetic sealing, a light exit surface of an external optical member such as a lens or a light guide plate, etc., it is usually 5% by weight or more, preferably 7% by weight or more, more preferably 10 % By weight or more, usually 90% by weight or less, preferably 80% by weight or less, more preferably 70% by weight or less.

  In addition, when the optical member comprising at least the polyorganosiloxane cured product of the present invention is used for a semiconductor light-emitting device in a sealing material, a packaging material, an adhesive (diebon agent), etc. In addition, inorganic particles may be further added. The technical significance of containing the inorganic particles and the details thereof are the same as those described above for the two-component composition.

[5] Embodiment of Semiconductor Light-Emitting Device As an example of the optical member of the present invention comprising at least the cured polyorganosiloxane of the present invention, a semiconductor light-emitting device comprising at least the optical member of the present invention (hereinafter referred to as “book” The semiconductor light-emitting device of the present invention is sometimes referred to as an example. In each of the following embodiments, the semiconductor light emitting device of the present invention may be abbreviated as “light emitting device” as appropriate.
Further, the optical member of the present invention used for the semiconductor light emitting device of the present invention is referred to as a semiconductor light emitting device member. Further, to which part the optical member of the present invention is used will be described collectively after the description of all the embodiments. However, these embodiments are merely used for convenience of explanation, and examples of the semiconductor light emitting device including at least the optical member of the present invention are not limited to these embodiments.

[5-1] Embodiment 1
In the light emitting device 1A of the present embodiment, as shown in FIG. 1, the light emitting element 2 is surface-mounted on an insulating substrate 16 provided with a printed wiring 17. In the light emitting element 2, a p-type semiconductor layer (not shown) and an n-type semiconductor layer (not shown) of the light emitting layer portion 21 are electrically connected to printed wirings 17 and 17 through conductive wires 15 and 15, respectively. Has been. The conductive wires 15 and 15 have a small cross-sectional area so as not to block light emitted from the light emitting element 2.

  Here, as the light emitting element 2, an element emitting light of any wavelength from the ultraviolet to the infrared range may be used, but here, a gallium nitride LED chip is used. In addition, the light emitting element 2 has an n-type semiconductor layer (not shown) formed on the lower surface side in FIG. 1 and a p-type semiconductor layer (not shown) formed on the upper surface side, and light output from the p-type semiconductor layer side. Therefore, the upper part of FIG.

  A frame-shaped frame member 18 surrounding the light emitting element 2 is fixed on the insulating substrate 16. The frame member 18 and the insulating substrate 16 may be configured as a package in which these are integrated. A sealing portion 19 that seals and protects the light emitting element 2 is provided inside the frame member 18. The sealing portion 19 is formed by the member for a semiconductor light emitting device according to the present invention, and can be formed by potting with the two-component composition of the present invention. The sealing part 19 may contain a phosphor for the purpose of functioning as a wavelength conversion member of the light emitting element 2.

Therefore, since the light emitting device 1A of the present embodiment includes the light emitting element 2 and the sealing portion 19 using the semiconductor light emitting device member, the light durability and the heat durability of the light emitting device 1A are improved. be able to. In addition, since cracks and peeling do not easily occur in the sealing portion 19, it is possible to increase the light transmittance of the light emitting element 2 in the sealing portion 3A.
Furthermore, light color unevenness and light color variation can be reduced as compared with the conventional case, and the light extraction efficiency can be increased. That is, since the sealing portion 19 can be made to have high light transmittance with respect to the light emitting element 2 without cloudiness or turbidity, the light color uniformity is excellent, and there is almost no light color variation between the light emitting devices 1A. The light extraction efficiency of the light emitting element 2 to the outside can be increased compared to the conventional case. In addition, the weather resistance of the luminescent material can be increased, and the life of the light emitting device 1A can be extended as compared with the conventional case.

Furthermore, in this embodiment, as shown in FIG. 1, the optical member 3A covers the front surface of the light emitting element 2, and the sealing portion 19 is formed on the optical member 3A with a material different from that of the optical member 3A. Is formed. The optical member 3A is used in the following applications, for example.
i) Transparent thin film that functions as a light extraction film and sealing film on the surface of the light emitting element 2 ii) A phosphor-containing thin film that functions as a wavelength converting member of the light emitting element 2 The optical member 3A is, for example, a chip of the light emitting element 2 It can form by apply | coating the raw material of said polyorganosiloxane hardened | cured material by spin coating etc. at the time of formation. The optical member 3A is used as necessary, and the light emitting device of the present invention may naturally be an embodiment that does not have this.

[5-2] Embodiment 2
The basic configuration of the light emitting device 1B of the present embodiment is substantially the same as that of the first embodiment, and as shown in FIG. There is a feature in that. In addition, the same code | symbol is attached | subjected to the component similar to Embodiment 1, and description is abbreviate | omitted.

The optical member 33 is used for the following applications, for example.
i) Lid that shields the light emitting device 1B from external oxygen and moisture ii) A phosphor-containing optical member that functions as a wavelength converting member of the light emitting element 2 That is, in i), the light emitting element 2 and the sealing portion 19 The upper surface side is shielded from oxygen and moisture in the outside by an optical member 33 as a transparent lid made of, for example, glass or highly airtight resin.

The optical member 33 and the sealing part 19 may be in direct contact or may have a gap, but a semiconductor light emitting device with high light extraction efficiency and high brightness can be obtained when there is no gap. When it has a space | gap, it is preferable to set it as vacuum sealing or inert gas enclosure.
In such an embodiment, since the optical member 33 suppresses the entry of external factors such as moisture and oxygen, which accelerate the deterioration of the phosphor and the sealing resin, and volatilization of the sealing resin decomposition gas due to heat and light. There is an advantage that the luminance reduction and shrinkage peeling of the sealing portion due to the can be reduced.

  In ii), the optical member 33 is excited by the light from the light emitting element 2 and emits light of a desired wavelength. In the case where the sealing part 19 is formed of an optical member that does not contain a phosphor, impurities due to heat generation or phosphor deterioration due to excitation of the phosphor than in the embodiment in which the phosphor is directly contained in the sealing part 19 It is preferable in that it is not damaged due to elution of selenium.

  Thus, in the light emitting device 1B of the present embodiment, the optical member 33 has not only a wavelength conversion function but also a function as a lens, and the directivity control of light emission by the lens effect can be performed. When the lens effect is not expected and only one or more of the above i) or ii) is expected, the optical member is not in a lens shape but may have a plate shape with a flat surface (upper surface). Good. Further, when the light extraction effect is expected, the surface (upper surface) may be formed to have an uneven shape instead of the lens shape.

  In addition, various embodiments of the light-emitting device of the present invention can be applied. For example, the light-emitting device can be applied as it is to those described in paragraphs [0395] to [0512] of Patent Document 3, and light emission whose design is appropriately changed. It can also be applied to devices.

[5-3] Application to Semiconductor Light-Emitting Device Member In the light-emitting device (semiconductor light-emitting device) of each of the first and second embodiments described above, the optical member for semiconductor light-emitting device according to the present invention (hereinafter simply “optical member”). The part to which is applied) is not particularly limited. In each of the above embodiments, the example in which the optical member according to the present invention is applied as the member that forms the sealing portion 19 has been described. However, in addition to this, for example, the above-described optical member 3A (FIG. 1), the optical member 33 (FIG. 2), the frame member 18 (FIGS. 1 and 2), the package (FIGS. 1 and 2) in which the frame member 18 and the insulating substrate 16 are integrated, and the like can be suitably used. By using the optical member according to the present invention as these members, various excellent sealing properties, transparency, light resistance, heat resistance, film-forming properties, cracks associated with long-term use, suppression of peeling, etc. An effect can be obtained. In addition, when the optical member of the present invention is used for a frame material, an insulating substrate, a package, etc., it is preferable to use these methods because it is excellent in moldability in transfer molding or LIM molding (Liquid Injection Mold molding). .

  Moreover, since the two-component composition of the present invention has good adhesion as described above, it can be used as an adhesive for semiconductor light emitting devices in addition to the above-described optical members. Specifically, for example, when bonding a semiconductor element and a package, when bonding a semiconductor element and a submount, when bonding package components, when bonding a semiconductor light emitting device and an external optical member, etc. The polyorganosiloxane cured product of the present invention can be used by coating, printing, potting and the like. The polyorganosiloxane cured product of the present invention is particularly excellent in light resistance and heat resistance. A semiconductor light emitting device having the same can be provided.

  The light-emitting device of the present invention can be used alone or in combination, for example, as an illumination lamp, a backlight for a liquid crystal panel, various illumination devices such as ultra-thin illumination, and an image display device. it can.

[6] Light Guide Plate As an example of the optical member of the present invention comprising at least the cured polyorganosiloxane of the present invention, a light guide plate comprising at least the optical member of the present invention (hereinafter referred to as “the light guide plate of the present invention” as appropriate). Will be explained).

  The two-component curable polyorganosiloxane composition or the polyorganosiloxane cured product of the present invention can be used as an optical member in an optical communication system, particularly in an optical transceiver module. Optical waveguides for transmitting optical signals require not only high productivity and low cost, but also various characteristics such as light transmission (transparency), light resistance, heat resistance, hydrothermal resistance, and UV resistance. The With the above characteristics, particularly in an optical apparatus, for example, when displaying a display unit of a display device such as a display, a button part of a facsimile, a telephone, a mobile phone, and other various home appliances, light emitted from a light source is desired. It is preferably used as a light guide plate that emits light at a site. Since the two-component curable polyorganosiloxane composition and the cured polyorganosiloxane of the present invention are excellent in transparency and can achieve a high refractive index as necessary, so-called light guide plates and optical waveguides are used as optical members. Suitable for the core layer (core part).

[7] Aerospace industry components
As an example of the optical member of the present invention comprising at least the polyorganosiloxane cured product of the present invention, an aerospace industrial member comprising at least the optical member of the present invention (hereinafter referred to as “aerospace industrial member of the present invention as appropriate”). ").
When the two-component curable polyorganosiloxane composition or the cured polyorganosiloxane of the present invention is used as an optical member, light transmittance (transparency), light resistance, heat resistance, hydrothermal resistance, UV resistance It can be used for materials for the aerospace industry where these characteristics are high and these characteristics are required. As materials for the aerospace industry, for example, it can be used as a static neutralizing material, conductive adhesive, gasket material, flash protection material, electromagnetic shielding material, tank material, rocket outer material, etc. by compositing with carbon nanomaterials can do.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, they are for the purpose of explaining the present invention, and are not intended to limit the present invention to these embodiments.

[1] Production and Evaluation of Liquid Composition (A) (Liquid A) [1-1] Pre-Liquid A Momentive Performance Materials Japan (Momentive Performance Materials Japan GK. Same as source) 2630 g of both-end silanol dimethyl silicone oil XC96-723, 70.22 g of methyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. and 1.89 g of zirconium tetraacetylacetonate powder manufactured by Matsumoto Fine Chemical Co., Ltd. as a catalyst The mixture was weighed in a 3 L five-necked flask equipped with a stirring blade, a fractionating tube, a Dimroth condenser, and a Liebig condenser, and stirred at room temperature for 15 minutes until the coarse particles of the catalyst were dissolved. Thereafter, the temperature of the reaction solution was raised to 100 ° C. to completely dissolve the catalyst, and initial hydrolysis was performed while stirring at 470 rpm for 30 minutes at 100 ° C. under total reflux.

Subsequently, the connection of the apparatus is reconnected from the total reflux so that the distillate comes out to the Liebig condenser side, nitrogen is blown into the liquid with SV20, and the generated methanol, water and by-product low boiling silicon components are accompanied with nitrogen. The mixture was stirred at 100 ° C. and 470 rpm for 1 hour while distilling off. The polymerization reaction was continued for 5 hours while raising and maintaining the temperature at 130 ° C. while blowing nitrogen into the liquid with SV20 to obtain a reaction liquid having a viscosity of 120 mPa · s. Here, “SV” is an abbreviation for “Space Velocity” and refers to the volume of blown volume per unit time. Therefore, SV20 refers to blowing N ₂ in a volume 20 times that of the reaction solution in one hour.

  Nitrogen blowing was stopped and the reaction solution was once cooled to room temperature, then divided and transferred to four 1 L eggplant-shaped flasks, and minutely at 65 ° C. each at 120 ° C. and 1 kPa on an oil bath using a rotary evaporator. The remaining methanol, water, and low boiling silicon component were distilled off, and pressure filtration was performed with a PTFE filter cloth having a mesh size of 3.0 μm to obtain a liquid having a static viscosity of 215 cp (pre-A liquid).

[1-2] Solution A-1 Charged to a stirring and mixing vessel provided with a stirring blade coated with Teflon (registered trademark) 2000 g of the pre-A solution obtained in [1-1] above, and activated carbon (manufactured by Nippon Enviro Chemicals) Purified white lees) 133.8 g was added and stirred at room temperature for 1 hour. No. Pressure filtration was performed with 5A filter paper. To the filtrate, 133.8 g of activated carbon was added again and No. It filtered with 5 A filter paper, and also A-1 liquid was obtained by implementing pressure filtration with the filter cloth made from PTFE with an opening of 0.1 micrometer. In addition, the static viscosity of A-1 liquid was static viscosity 232cp.

When the polyorganosiloxane compound contained in the liquid A-1 was evaluated by liquid Si-NMR, it was found to be a compound represented by the following general formula (2). R ¹³ is a methyl group, R ¹⁴ is a methyl group, R ¹⁵ is a group selected from a methyl group, a hydroxyl group, and a methoxy group, R ¹⁶ and R ¹⁷ are methyl groups, and R ¹⁸ is a methyl group, a hydroxyl group, and a methoxy group. This compound has two or more silanol groups in one molecule, and p = 0.014, q = 0.964, and r = 0.022.

The pre-A solution and the A-1 solution after removal of the catalyst were each dissolved in n-heptane for absorptiometry to give a 2 wt% solution, and the ultraviolet absorption spectrum was measured using a quartz cell having an optical path length of 1 cm. It was confirmed that the absorption peak at 271 nm derived from the acetylacetone ligand disappeared as the catalyst was removed.
Moreover, when the density | concentration of Pt and Zr contained in A-1 liquid was confirmed by the ICP emission spectrometry, Pt was 1 ppm or less and Zr was 13 ppm.

  In addition, 2 g of pre-A liquid was placed in a 5 cmφ Teflon petri dish and kept at 150 ° C. for 3 hours with a thermostatic chamber. It was. From this, it is considered that Zr remaining in the liquid A loses acetylacetone, which is a ligand, in the synthesis process, and binds to the polyorganosiloxane chain or becomes a form close to zirconium oxide and is deactivated.

Furthermore, the storage stability at room temperature of Pre-A liquid and A-1 liquid was evaluated.
When stored at room temperature, the pre-A solution increased in static viscosity by 2 times or more in 1 month and by 3 times or more in 2 months. On the other hand, when the A-1 solution was stored at room temperature (25 ° C.), the static viscosity was hardly increased to 1.06 times even when stored for 8 months. There was no change in visual appearance.

[1-3] Liquid A-2 In a 20 mL screw tube, 10 g of the liquid A-1 described above, consisting of only trifunctional silicon as a silicone-based curing accelerator, and the organic groups bonded to silicon are a methyl group and a methoxy group. An organosiloxane oligomer (methoxy group content 45 wt%, weight average molecular weight 500) (commercially available product) 0.02 g was charged and stirred at room temperature for 30 minutes to prepare A-2 solution containing a curing accelerator. .

[2] Production and Evaluation of Liquid Composition (B) (Liquid B) [2-1] Liquid B-1 40 g of a methyl / hydride silicone oil KF-99 manufactured by Shin-Etsu Chemical Co. As a sample, 0.8 g of zirconium tetraacetylacetonate powder manufactured by Matsumoto Fine Chemical Co., Ltd. was charged and stirred at room temperature for 30 minutes. It was filtered under pressure with a PTFE filter cloth having an opening of 1 μm to obtain a solution B-1.

  Liquid B-1 (static viscosity immediately after preparation is 18.4 cp), when stored at room temperature (25 ° C.), the static viscosity does not increase as much as 23.6 cp (1.28 times immediately after adjustment) even after storage for 6 months. It was. Further, even when stored at room temperature for 5 months and further at 50 ° C. for 1 month, the static viscosity was 28.4 cp (1.54 times) and the thickening level was small. There was no change in visual appearance.

[2-2] B-2 solution A 100 mL screw tube is charged with 40 g of methyl / hydride silicone oil KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd. and 0.8 g of zirconium tetraacetylacetonate powder manufactured by Matsumoto Fine Chemical Co., Ltd. as a catalyst component. The mixture was stirred at room temperature for 30 minutes. It was filtered under pressure with a PTFE filter cloth having an opening of 1 μm to obtain a liquid B-2.

  Liquid B-2 (static viscosity immediately after preparation was 16.7 cp) did not increase at all to 15.0 cp when stored for 6 months when stored at room temperature (25 ° C.). Further, even when stored at room temperature for 5 months and further at 50 ° C. for 1 month, the static viscosity did not increase at all to 16.4 cp. There was no change in visual appearance.

[2-3] B-3 solution In a 50 mL screw tube, 25 g of methyl / hydride silicone oil KF-99 manufactured by Shin-Etsu Chemical Co., Ltd., zirconium 2-ethylhexanoate manufactured by STREM as a catalyst component (6 wt% as Zr) 1.0 g of mineral spirit solution) was added, and the mixture was stirred for 30 minutes in the air at room temperature to obtain B-3 solution.

  When the B-3 solution (static viscosity immediately after preparation was 17.7 cp) was stored at room temperature (25 ° C.), the static viscosity did not increase at all to 16.5 cp even after 6 months. Further, even when stored at room temperature for 5 months and further at 50 ° C. for 1 month, the static viscosity was 18.2 cp (1.03 times immediately after adjustment) and the level of thickening was slight. There was no change in visual appearance.

[2-4] B-4 solution In a 50 mL screw tube, 25 g of methyl / hydride silicone oil KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd., zirconium 2-ethylhexanoate manufactured by STREM as a catalyst component (6 wt% as Zr) 1.0 g of mineral spirit solution) was added and stirred at room temperature for 30 minutes to obtain B-4 solution.

  When the B-4 solution (static viscosity immediately after preparation was 15.0 cp) was stored at room temperature (25 ° C.), the static viscosity did not increase to 14.1 cp even when stored for 6 months. Further, even when stored at room temperature for 5 months and further at 50 ° C. for 1 month, the static viscosity did not increase at all to 14.2 cp. There was no change in visual appearance.

[2-5] B-5 solution In a 50 mL screw tube, 24.5 g of methyl / hydride silicone oil KF-9901 manufactured by Shin-Etsu Chemical Co., Ltd. and zirconium 2-ethylhexoate (Zr) manufactured by Nippon Chemical Industry Co., Ltd. as a catalyst component As a 12 wt% mineral spirit solution) and stirred at room temperature for 30 minutes to obtain a B-5 solution.

  When the B-5 solution (static viscosity immediately after preparation was 16.5 cp) was stored at room temperature (25 ° C.), the static viscosity did not increase at all to 16.3 cp even after 1.5 months. Further, even when stored at room temperature for 1 month and further at 50 ° C. for 10 days, the static viscosity did not increase at all to 16.4 cp. There was no change in visual appearance.

[2-6] B-6 solution In a 20 mL screw tube, 8 g of methyl / hydride silicone oil HMS-064 manufactured by Gelest, zirconium 2-ethylhexanoate manufactured by STREM as a catalyst component (6 wt% mineral as Zr) (Spirit solution) was charged in an amount of 0.32 g, and stirred at room temperature for 30 minutes to obtain a B-6 solution.

  When the B-9 solution (static viscosity immediately after preparation was 5846 cp) was stored at room temperature (25 ° C.), the static viscosity did not increase at all to 5952 cp (1.02 times) even after storage for 4 months. Further, even when stored at room temperature for 3 months and further at 50 ° C. for 35 days, the static viscosity was 6131 cp (1.05 times) and did not increase at all. There was no change in visual appearance.

[2-7] B-7 solution In a 20 mL screw tube, 10 g of methyl / hydride silicone oil HMS-064 manufactured by Gelest, and zirconium 2-ethylhexoate manufactured by DIC as a catalyst component (12 wt% mineral as Zr) 0.4 g of a spirit solution) was added and stirred at room temperature for 30 minutes to obtain a B-7 solution.

[2-8] B-8 solution In a 20 mL screw tube, 10 g of methyl / hydride silicone oil HMS-071 manufactured by Gelest, zirconium 2-ethylhexoate manufactured by DIC as a catalyst component (12 wt% mineral as Zr) 0.4 g of spirit solution) was added and stirred at room temperature for 30 minutes to obtain a B-8 solution.

[2-9] B-9 solution In a 20 mL screw tube, 10 g of both ends hydride modified dimethyl silicone oil DMS-H41 manufactured by Gelest, zirconium 2-ethylhexoate manufactured by DIC as a catalyst component (12 wt% as Zr) 0.4 g of mineral spirit solution) was added, and the mixture was stirred for 30 minutes at room temperature in the atmosphere to obtain B-9 solution.

[2-10] B-10 solution A 200 mL glass bottle is charged with 98 g of both-end silanol dimethyl silicone oil YF-3800 manufactured by Momentive Performance Materials Japan GK, and 2 g of zirconium tetraacetylacetonate powder manufactured by Matsumoto Fine Chemical Co., Ltd. as a catalyst component. The mixture was stirred at room temperature for 30 minutes. It was filtered under pressure with a PTFE filter cloth having an opening of 3 μm to obtain a B-10 solution.

  When the B-10 solution (static viscosity immediately after preparation was 71.1 cp) was stored at 8 ° C., the static viscosity did not increase at all to 80.5 cp (1.13 times) even when stored for 8 months. There was no particular change in visual appearance.

[2-11] B-11 solution A 50 mL screw tube is charged with 20 g of heptane manufactured by Kishida Chemical Co., Ltd. and 0.4 g of zirconium tetraacetylacetonate powder manufactured by Matsumoto Fine Chemical Co., Ltd. as a catalyst component, and stirred at room temperature for 30 minutes. did. It was filtered under pressure with a PTFE filter cloth having an opening of 3 μm to obtain a B-11 solution.

[2-12] B-12 solution In a 50 mL screw tube, 20 g of heptane manufactured by Kishida Chemical Co., Ltd. and 0.4 g of zirconium 2-ethylhexanoate manufactured by STREM as a catalyst component (6 wt% mineral spirit solution as Zr) The mixture was stirred and stirred at room temperature for 30 minutes to obtain a B-12 solution.

[2-13] B-13 solution In a 20 mL screw tube, 10 g of side chain carbinol-modified silicone X-22-4039 manufactured by Shin-Etsu Chemical Co., Ltd., zirconium 2-ethylhexoate manufactured by DIC as a catalyst component (12 wt. As Zr) % Mineral spirit solution) was charged and stirred at room temperature for 30 minutes to obtain a B-13 solution.

  When the B-13 solution (static viscosity immediately after preparation was 69.0 cp) was stored at room temperature (25 ° C.), the static viscosity did not increase at all to 70.7 cp (1.02 times) even when stored for 4 months. Further, even when stored at room temperature for 3 months and further at 50 ° C. for 35 days, the static viscosity did not increase at all to 70.9 cp (1.03 times). There was no change in visual appearance.

[2-14] B-14 solution In a 20 mL screw tube, 10 g of both-end carbinol-modified silicone X-22-160AS manufactured by Shin-Etsu Chemical Co., Ltd., DIC Zirconium 2-ethylhexoate (Zr: 12 wt. % Mineral spirit solution) was charged and stirred at room temperature for 30 minutes to obtain B-14 solution.

  When the B-14 liquid (static viscosity immediately after preparation was 32.4 cp) was stored at room temperature (25 ° C.), the static viscosity did not increase at all to 32.6 cp (1.01 times) even after storage for 4 months. Further, even when stored at room temperature for 3 months and further at 50 ° C. for 35 days, the static viscosity was 32.5 cp (1.00 times) and the viscosity did not increase at all. There was no change in visual appearance.

[2-15] B-15 solution 10 g of a side chain carbinol-modified silicone X-22-4015 manufactured by Shin-Etsu Chemical Co., Ltd. as a catalyst component, zirconium 2-ethylhexoate manufactured by DIC (12 wt. As Zr) in a 20 mL screw tube % Mineral spirit solution) was charged and stirred at room temperature for 30 minutes to obtain a B-15 solution.

  When the B-15 solution (static viscosity immediately after preparation was 110.5 cp) was stored at room temperature (25 ° C.), the static viscosity did not increase at all to 112.8 cp (1.02 times) even after storage for 3 months. Further, even when stored at room temperature for 2 months and further at 50 ° C. for 24 days, the static viscosity was 115.3 cp (1.04 times) and did not increase at all. There was no change in visual appearance.

[2-16] B-16 solution In a 20 mL screw tube, 10 g of Shin-Etsu Chemical's one-end carbinol-modified silicone X-22-170DX, DIC Zirconium 2-ethylhexoate (12 wt. As Zr) was used as a catalyst component. % Mineral spirit solution) was charged and stirred at room temperature for 30 minutes to obtain a B-16 solution.

  When the B-16 solution (static viscosity immediately after preparation was 59.9 cp) was stored at room temperature (25 ° C.), the static viscosity did not increase at all to 59.4 cp even after storage for 3 months. Further, even when stored at room temperature for 2 months and further at 50 ° C. for 24 days, the static viscosity was 61.3 cp (1.02 times), and the viscosity did not increase at all. There was no change in visual appearance.

[2-17] B-17 solution Into a 20 mL screw tube, 9.6 g of n-dodecane manufactured by Kishida Chemical Co., Ltd., zirconium 2-ethylhexoate manufactured by Nippon Chemical Industry Co., Ltd. (12 wt% mineral spirit solution as Zr) ) And stirred for 30 minutes at room temperature to obtain a B-17 solution.

  The B-17 solution had no change in visual appearance even when stored in a sealed 50 cc screw bottle at room temperature (25 ° C.) for 3 months. The same was true for products stored at 50 ° C for 3 months.

[3] Production of two-component composition (mixed solution) and polysiloxane cured product [3-1] Examples 1 to 17
In a 20 mL screw tube, the above-mentioned A liquid (A-1 liquid) 6g and the above-mentioned B liquid (B-1-B-17 liquid) 0.3g each (A liquid / B liquid = 20/1) The mixture was stirred at room temperature for 30 minutes to obtain a two-component curable polysiloxane composition (mixed solution) of Examples 1 to 17.
2 g of each mixed solution was put in a Teflon (registered trademark) petri dish having a diameter of 5 cm and held at 150 ° C. in an explosion-proof furnace for 3 hours to obtain a colorless and transparent elastomeric film made of the cured polysiloxane of Examples 1 to 17. . The weight retention rate before and after the curing operation was 93% or more, and the hardness was 20 in Shore A.

[3-2] Example 18
As Example 18, a two-component composition containing a silicone curing accelerator was evaluated. A 20 mL screw tube was charged with 6 g of the aforementioned A-2 solution as the A solution and 0.3 g of the aforementioned B-17 solution as the B solution (A solution / B solution = 20/1), and 30 at room temperature in the atmosphere. The mixture was stirred for a while to obtain a two-component curable polysiloxane composition (mixed solution) of Example 18. 2 g of the mixed solution of Example 18 was put in a Teflon (registered trademark) petri dish having a diameter of 5 cm and held at 150 ° C. in an explosion-proof furnace, and the hardness of the cured product was measured using a durometer type A hardness meter. The curing rate was compared with Example 17 in which no curing accelerator was added.
The two-component composition of Example 17 reached a hardness of 20 in 3 hours and a hardness of 21 in 4 hours after holding at 150 ° C., and remained unchanged thereafter. On the other hand, the two-part composition of Example 18 containing a silicone curing accelerator reached a hardness of 21 in 1 hour after holding at 150 ° C., and thereafter the hardness was stable. The cured polysiloxane product of Example 18 after sufficiently curing was a colorless and transparent elastomeric film similar to Example 17.

[4] Evaluation of cured polysiloxane [4-1] UV resistance of cured polysiloxane The evaluation of UV resistance of the cured polysiloxane was an independent cured film having a smooth surface formed to a thickness of about 1 mm or more. As a sample, UV irradiation was performed using a UV irradiation apparatus (Icure ANUP5204) manufactured by Matsushita Electric Works & Vision. Light of 250 nm or less was cut with a filter, and irradiation / measurement was performed with the distance from the sample to the optical fiber being 2 mm including the filter thickness.
Table 1 shows the results of UV resistance tests performed on the polysiloxane cured products of Examples 1 to 18.

  Even when any of the polysiloxane cured products of Examples 1 to 18 was irradiated for 20 hours, no discoloration or cracking occurred.

[4-2] Heat resistance and hydrothermal resistance of polysiloxane cured product The heat resistance and hydrothermal resistance of the polysiloxane cured product are as follows. Was stored at 500 ° C. and normal humidity and hydrothermal resistance was stored at 85 ° C. and 85% RH (relative humidity) for 500 hours, and the weight loss rate before and after the storage was evaluated.
Table 1 shows the results of evaluating the polysiloxane cured products of Examples 1 to 18.

  Each of the cured polysiloxanes of Examples 1 to 18 showed a weight retention of 85% or more at 200 ° C., 90% or more at 85 ° C. and 85% RH after storage for 500 hours, No cracks or major hardness changes occurred.

[5] Hygroscopic reflow test and heat cycle test The following hygroscopic reflow test and heat cycle test (evaluation example) were conducted for the purpose of examining the durability of the LED package for applicability to the semiconductor light emitting device of the present invention. Carried out.

[5-1] Hygroscopic Reflow Test The two-component curable polysiloxane compositions (mixed solutions) of Examples 1 to 14 and Examples 17 and 18 were used for LED packages on a silver surface and LEDs on a ceramic (alumina) surface. Each of the 10 packages was applied.
The mixture was cured by heating in air at 90 ° C. for 2 hours, then at 110 ° C. for 1 hour, and further at 150 ° C. for 3 hours to cure the cured products of Examples 1-14 and Examples 17 and 18. A package for LED containing was obtained.
The obtained LED package was moisture-absorbed at 85 ° C./85% RH for 24 hours, and then heated at 260 ° C. for 1 minute, and the number of LED packages from which the resin peeled from the package surface was confirmed. The results are shown in Table 1.
After the moisture absorption operation and after heating at 260 ° C., no peeling was confirmed from the package on either the silver surface or the ceramic surface.

[5-2] Heat cycle test Using the two-component curable polysiloxane compositions (mixed solutions) of Examples 1 to 8, Examples 10 to 14, and Examples 17 and 18, the same as the moisture absorption reflow test described above. The LED package was obtained by the method. This LED package was exposed to heating / cooling conditions of 120 ° C. for 10 minutes and −50 ° C. for 10 minutes. After 500 cycles of the heating / cooling conditions, the number of LED packages from which the resin peeled from the package surface was confirmed. As a result, no peeling was confirmed for any of the LED packages on the surface.

[6] Semiconductor Light-Emitting Device (LED) Test Regarding the applicability of the present invention to the semiconductor light-emitting device, the following test was conducted for the purpose of examining the performance of the semiconductor light-emitting device (LED) itself.
The red phosphor Ca _0.87 Eu _0.008 Al _0.88 Si _1.12 O manufactured by Mitsubishi Chemical Corporation was added to the two-component curable polysiloxane compositions (mixed solutions) of Examples 1-4, Examples 10-12, and Examples 17 and 18. _0.12 N _2.88 , green phosphor (Ba, Sr, Eu) ₂ SiO ₄ , blue phosphor Ba _0.7 Eu _0.3 MgAl ₁₀ O ₁₇ , and AEROSIL RX-200 manufactured by Evonik as a thixotropic agent were mixed to form a paste. This paste was potted in a silver surface package on which a near ultraviolet LED having a peak wavelength at 405 nm was mounted in the same manner as in the moisture absorption reflow test described above, and cured to produce a semiconductor light emitting device (LED). The luminance maintenance rate of the LED was measured over time under each environmental condition of 25 ° C./55% RH, 60 ° C./90% RH, and 85 ° C. The results are shown in FIGS. As shown in the graph, a high luminous flux maintenance factor was observed when any material was used.

  Moreover, about the two-component curable polysiloxane composition (mixed solution) of Example 10-2 prepared using the B-10 solution stored at 8 ° C. for 4 months and the A-1 solution, A phosphor paste was prepared in the same manner as described above. About this fluorescent substance paste, LED was produced and the brightness | luminance maintenance factor was measured. The results are shown in FIG. As the graph shows, a high luminous flux maintenance factor was recognized even when a two-component composition stored for a long time was used.

Reference Example 1: Storage stability of liquid mixture of liquid A and liquid B In a 20 mL screw tube, 6 g of the liquid A-1 described above and 0.3 g of the liquid B-1 to B-17 described above (liquid A / B liquid = 20/1) The mixture was stirred and stirred at room temperature for 30 minutes to obtain a curable polysiloxane composition (mixed liquids 1 to 17) for a storage stability test as a reference example. When the obtained mixed liquids 1 to 17 were each stored at 25 ° C., it was confirmed that each of the 25 ° C. stored products increased in static viscosity to 2 times or more in one month and could not be stored at room temperature for a long time.

Reference Example 2: Example of one-part composition Reference Example 2-1
In a 200 mL glass bottle, 97.7 g of both-end silanol dimethyl silicone oil YF-3057 manufactured by Momentive Performance Materials, 0.06 g of tin octylate manufactured by Wako Pure Chemical Industries, Ltd. as a catalyst component, methyl / hydride silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. 2.28 g of KF-9901 was charged all at once and stirred at room temperature for 30 minutes to obtain a curable polysiloxane composition of Reference Example 2-1. The composition solution stored at room temperature gelled the next day.

Reference Example 2-2
In a 50 mL screw tube, 20 g of both-end silanol dimethyl silicone oil YF-3057 manufactured by Momentive Performance Materials, 0.06 g of diethylammonium hydroxide manufactured by Tokyo Chemical Industry Co., Ltd. as a catalyst component, and methyl / hydride silicone oil KF manufactured by Shin-Etsu Chemical Co., Ltd. -9901 was charged all at once, and stirred at room temperature for 30 minutes to obtain a curable polysiloxane composition of Reference Example 2-2. The composition liquid stored at room temperature gelled after 2 hours.

Reference Example 2-3
10 g of both-end silanol dimethyl silicone oil YF-3057 manufactured by Momentive Performance Materials, 0.01 g of tin compound Neostan U-810 manufactured by Nitto Kasei Co., Ltd. as a catalyst component, and methyl / hydride silicone manufactured by Shin-Etsu Chemical Co., Ltd. 0.23 g of oil KF-9901 was charged all at once and stirred at room temperature for 30 minutes to obtain a curable polysiloxane composition of Reference Example 2-3. The composition liquid stored at −15 ° C. was partially gelated and clouded within 7 days.

Reference Example 3: Semiconductor light emitting device (LED) test (pre-A liquid)
In place of the two-component curable polysiloxane composition (mixed solution) of the example, except that the pre-A solution was used, the same production method as in the above [6] semiconductor light emitting device (LED) test was used. A semiconductor light emitting device (LED) of Example 3 was obtained. The luminance maintenance rate of the LED was measured over time under each environmental condition of 25 ° C./55% RH, 60 ° C./90% RH, and 85 ° C. The results are shown in FIG.

  The use of the two-component curable polyorganosiloxane composition and the cured polyorganosiloxane of the present invention is not particularly limited, but is suitable for a sealing material, a packaging material, an adhesive, etc. in the semiconductor field, particularly in the semiconductor light emitting device field. Can be used. Therefore, it can be suitably used in a wide range of fields in which the semiconductor light emitting device is used, that is, a light source for a liquid crystal backlight such as a lighting device, an image display device, and a thin television.

  In addition, the two-component curable polyorganosiloxane composition and the polyorganosiloxane cured product of the present invention are not limited to the field of semiconductor light emitting devices described above, but also include light transmittance (transparency), light resistance, heat resistance, and water resistance. Aerospace industry materials that require various properties such as heat resistance and UV resistance, and other materials such as heat conductive sheets, heat conductive adhesives, insulating heat conductive materials, underfill materials, sealants, Aerospace because of its high applicability to optical waveguide structures, light guide plates, light guide sheets, reflected light control materials, diagnostic microfluid materials, microbial culture media, nanoimprint materials, outdoor building materials, and coating materials -The industrial applicability is extremely high in each field such as optics, electrical electronics, and biotechnology.

1,1A, 1B Light emitting device (semiconductor light emitting device)
2 Light-Emitting Element 3A Optical Member (Semiconductor Light-Emitting Device Member)
DESCRIPTION OF SYMBOLS 15 Conductive wire 16 Insulating board 17 Printed wiring 18 Frame material 19 Sealing part 33 Optical member (member for semiconductor light-emitting devices)

1 is a schematic cross-sectional view showing a first embodiment. FIG. 6 is a schematic cross-sectional view showing a second embodiment. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 1. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 2. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 3. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 4. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Reference Example 10. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 11. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 12. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 17. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example 18. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of Reference Example 10-2. It is a graph which shows the measurement result of the luminous flux maintenance factor of the semiconductor light-emitting device (LED) of the reference example III .

[3] Production of two-component composition (mixed solution) and polysiloxane cured product [3-1] Reference Examples 1 to 12, Examples 13 to 16, and Reference Example 17
In a 20 mL screw tube, the above-mentioned A liquid (A-1 liquid) 6g and the above-mentioned B liquid (B-1-B-17 liquid) 0.3g each (A liquid / B liquid = 20/1) The mixture was stirred at room temperature for 30 minutes to obtain a two-component curable polysiloxane composition (mixed solution) of Reference Examples 1 to 12, Examples 13 to 16, and Reference Example 17 .
2 g of each mixed solution was put into a Teflon (registered trademark) petri dish having a diameter of 5 cm and held at 150 ° C. for 3 hours in an explosion-proof furnace. From the polysiloxane cured products of Reference Examples 1 to 12, Examples 13 to 16, and Reference Example 17 A colorless and transparent elastomeric film was obtained. The weight retention rate before and after the curing operation was 93% or more, and the hardness was 20 in Shore A.

[3-2] Reference Example 18
As Reference Example 18, a two-component composition containing a silicone curing accelerator was evaluated. A 20 mL screw tube was charged with 6 g of the aforementioned A-2 solution as the A solution and 0.3 g of the aforementioned B-17 solution as the B solution (A solution / B solution = 20/1), and 30 at room temperature in the atmosphere. The mixture was stirred for a while to obtain a two-component curable polysiloxane composition (mixed solution) of Example 18. 2 g of the mixed solution of Reference Example 18 was placed in a Teflon (registered trademark) petri dish having a diameter of 5 cm and held at 150 ° C. in an explosion-proof furnace, and the hardness of the cured product was measured using a durometer type A hardness meter. The curing rate was compared with Reference Example 17 in which no curing accelerator was added.
The two-part composition of Reference Example 17 reached a hardness of 20 in 3 hours and a hardness of 21 in 4 hours after holding at 150 ° C., and remained unchanged thereafter. On the other hand, the two-component composition of Reference Example 18 containing a silicone curing accelerator reached a hardness of 21 in 1 hour after being kept at 150 ° C., and thereafter the hardness was stable. The cured polysiloxane of Reference Example 18 after sufficiently curing was a colorless and transparent elastomeric film similar to Reference Example 17.

[4] Evaluation of cured polysiloxane [4-1] UV resistance of cured polysiloxane The evaluation of UV resistance of the cured polysiloxane was an independent cured film having a smooth surface formed to a thickness of about 1 mm or more. As a sample, UV irradiation was performed using a UV irradiation apparatus (Icure ANUP5204) manufactured by Matsushita Electric Works & Vision. Light of 250 nm or less was cut with a filter, and irradiation / measurement was performed with the distance from the sample to the optical fiber being 2 mm including the filter thickness.
Table 1 shows the results of UV resistance tests performed on the polysiloxane cured products of Reference Examples 1 to 12, Examples 13 to 16, and Reference Examples 17 and 18 .

None of the cured polysiloxanes of Reference Examples 1 to 12, Examples 13 to 16, and Reference Examples 17 and 18 were discolored or cracked even when irradiated for 20 hours.

[4-2] Heat resistance and hydrothermal resistance of polysiloxane cured product The heat resistance and hydrothermal resistance of the polysiloxane cured product are as follows. Was stored at 500 ° C. and normal humidity and hydrothermal resistance was stored at 85 ° C. and 85% RH (relative humidity) for 500 hours, and the weight loss rate before and after the storage was evaluated.
Table 1 shows the results of evaluating the cured polysiloxanes of Reference Examples 1 to 12, Examples 13 to 16, and Reference Examples 17 and 18 .

The polysiloxane cured products of Reference Examples 1 to 12, Examples 13 to 16, and Reference Examples 17 and 18 are all stored for 500 hours, and are at least 85% at 200 ° C. and 90% at 85 ° C. and 85% RH. % Or more, and no discoloration, cracking, or great hardness change occurred.

[5-1] Moisture absorption reflow test
The two-part curable polysiloxane compositions (mixed liquids) of Reference Examples 1 to 12, Examples 13 and 14, and Reference Examples 17 and 18 were used for a silver surface LED package and a ceramic (alumina) surface LED package. It applied to every 10 pieces.
The mixture was cured by heating at 90 ° C. for 2 hours, then at 110 ° C. for 1 hour, and further at 150 ° C. for 3 hours to cure the mixed solutions to Reference Examples 1 to 12, Examples 13, 14 and Reference Examples. An LED package containing 17, 18 cured products was obtained.
The obtained LED package was moisture-absorbed at 85 ° C./85% RH for 24 hours, and then heated at 260 ° C. for 1 minute, and the number of LED packages from which the resin peeled from the package surface was confirmed. The results are shown in Table 1.
After the moisture absorption operation and after heating at 260 ° C., no peeling was confirmed from the package on either the silver surface or the ceramic surface.

[5-2] Heat cycle test
Using the two-component curable polysiloxane compositions (mixed liquids) of Reference Examples 1 to 8, Reference Examples 10 to 12, Examples 13 and 14, and Reference Examples 17 and 18, in the same manner as the moisture absorption reflow test described above. An LED package was obtained. This LED package was exposed to heating / cooling conditions of 120 ° C. for 10 minutes and −50 ° C. for 10 minutes. After 500 cycles of the heating / cooling conditions, the number of LED packages from which the resin peeled from the package surface was confirmed. As a result, no peeling was confirmed for any of the LED packages on the surface.

[6] Semiconductor Light-Emitting Device (LED) Test Regarding the applicability of the present invention to the semiconductor light-emitting device, the following test was conducted for the purpose of examining the performance of the semiconductor light-emitting device (LED) itself.
The red phosphor Ca _0.87 Eu _0.008 Al _0.88 Si _1.12 O manufactured by Mitsubishi Chemical Corporation was added to the two-component curable polysiloxane compositions (mixed solutions) of Reference Examples 1 to 4, Reference Examples 10 to 12, and Reference Examples 17 and 18. _0.12 N _2.88 , green phosphor (Ba, Sr, Eu) ₂ SiO ₄ , blue phosphor Ba _0.7 Eu _0.3 MgAl ₁₀ O ₁₇ , and AEROSIL RX-200 manufactured by Evonik as a thixotropic agent were mixed to form a paste. This paste was potted in a silver surface package on which a near ultraviolet LED having a peak wavelength at 405 nm was mounted in the same manner as in the moisture absorption reflow test described above, and cured to produce a semiconductor light emitting device (LED). The luminance maintenance rate of the LED was measured over time under each environmental condition of 25 ° C./55% RH, 60 ° C./90% RH, and 85 ° C. The results are shown in FIGS. As shown in the graph, a high luminous flux maintenance factor was observed when any material was used.

Moreover, about the two-component curable polysiloxane composition (mixed solution) of Reference Example 10-2 prepared by using the B-10 solution stored at 8 ° C. for 4 months and the A-1 solution, A phosphor paste was prepared in the same manner as described above. About this fluorescent substance paste, LED was produced and the brightness | luminance maintenance factor was measured. The results are shown in FIG. As the graph shows, a high luminous flux maintenance factor was recognized even when a two-component composition stored for a long time was used.

Reference Example I : Storage stability of liquid mixture of liquid A and liquid B In a 20 mL screw tube, 6 g of the liquid A-1 described above and 0.3 g of the liquid B-1 to B-17 described above (liquid A / B liquid = 20/1) The mixture was stirred and stirred at room temperature for 30 minutes to obtain a curable polysiloxane composition (mixed liquids 1 to 17) for a storage stability test as a reference example. When the obtained mixed liquids 1 to 17 were each stored at 25 ° C., it was confirmed that each of the 25 ° C. stored products increased in static viscosity to 2 times or more in one month and could not be stored at room temperature for a long time.

Reference Example II : Example of 1-component composition Reference Example II- 1
In a 200 mL glass bottle, 97.7 g of both-end silanol dimethyl silicone oil YF-3057 manufactured by Momentive Performance Materials, 0.06 g of tin octylate manufactured by Wako Pure Chemical Industries, Ltd. as a catalyst component, methyl / hydride silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. 2.28 g of KF-9901 was charged all at once and stirred at room temperature for 30 minutes to obtain a curable polysiloxane composition of Reference Example II- 1. The composition solution stored at room temperature gelled the next day.

Reference Example II- 2
In a 50 mL screw tube, 20 g of both-end silanol dimethyl silicone oil YF-3057 manufactured by Momentive Performance Materials, 0.06 g of diethylammonium hydroxide manufactured by Tokyo Chemical Industry Co., Ltd. as a catalyst component, and methyl / hydride silicone oil KF manufactured by Shin-Etsu Chemical Co., Ltd. -9901 was charged all at once, and stirred at room temperature for 30 minutes to obtain a curable polysiloxane composition of Reference Example II- 2. The composition liquid stored at room temperature gelled after 2 hours.

Reference Example II- 3
10 g of both-end silanol dimethyl silicone oil YF-3057 manufactured by Momentive Performance Materials, 0.01 g of tin compound Neostan U-810 manufactured by Nitto Kasei Co., Ltd. as a catalyst component, and methyl / hydride silicone manufactured by Shin-Etsu Chemical Co., Ltd. 0.23 g of oil KF-9901 was charged all at once and stirred at room temperature for 30 minutes to obtain a curable polysiloxane composition of Reference Example II- 3. The composition liquid stored at −15 ° C. was partially gelated and clouded within 7 days.

Reference Example III : Semiconductor Light Emitting Device (LED) Test (Pre-A Liquid)
In place of the two-component curable polysiloxane composition (mixed solution) of the example, except that the pre-A solution was used, the same production method as in the above [6] semiconductor light emitting device (LED) test was used. A semiconductor light emitting device (LED) of Example III was obtained. The luminance maintenance rate of the LED was measured over time under each environmental condition of 25 ° C./55% RH, 60 ° C./90% RH, and 85 ° C. The results are shown in FIG.

Claims (15)

A two-component curable polyorganosiloxane composition for a semiconductor light-emitting device member, comprising the following liquid composition (A) and liquid composition (B).
Liquid composition (A): a liquid composition containing a polyorganosiloxane compound containing two or more silanol groups in one molecule and substantially free of a condensation catalyst. Liquid composition (B): a condensation catalyst; A polyorganosiloxane compound containing two or more substituents that react with a silanol group in one molecule, the substituent that reacts with the silanol group is an organic group containing a hydroxyl group, and platinum (Pt) Liquid composition not substantially contained The two-component curable polyorganosiloxane composition according to claim 1, wherein the liquid composition (A) contains a compound represented by the following general formula (2).
(In the general formula (2), R ^{13 to} R ¹⁸ each independently represents a group selected from a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group and an aryl group. Moreover, p, q and r are Represents a number greater than or equal to 0, and p + q + r = 1.)   The two-component curable polyorganosiloxane composition according to claim 1 or 2, wherein at least one of the liquid composition (A) and the liquid composition (B) further contains inorganic particles.   The two-component curable poly (1) according to any one of claims 1 to 3, wherein a silicone-based crosslinking accelerator is contained in at least one of the liquid composition (A) and the liquid composition (B). Organosiloxane composition.   5. The two-component curing according to claim 4, wherein the silicone-based crosslinking accelerator is an organosiloxane oligomer containing trifunctional or higher functional silicon, wherein the oligomer has a weight average molecular weight of 200 or more and 100,000 or less. Polyorganosiloxane composition.   The two-component curable polyorganosiloxane according to claim 4 or 5, wherein the content of the silicone-based crosslinking accelerator is in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the liquid composition (A). Composition.   The liquid composition (A) is obtained by removing the condensation catalyst using an adsorptive substance, wherein the two-part curable polyorganosiloxane composition according to any one of claims 1 to 6 is used. Production method.   A polyorganosiloxane curing comprising a step of mixing and curing the liquid composition (A) and the liquid composition (B) in the two-component curable polyorganosiloxane composition according to any one of claims 1 to 6. Manufacturing method.   The method for producing a cured polyorganosiloxane according to claim 8, wherein the liquid composition (A) is obtained by removing the condensation catalyst using an adsorbent substance.   A cured polyorganosiloxane obtained by curing the two-component curable polyorganosiloxane composition according to any one of claims 1 to 6.   The optical member containing the polyorganosiloxane hardened | cured material of Claim 10.   The member for aerospace industry containing the polyorganosiloxane hardened | cured material of Claim 10.   A semiconductor light emitting device comprising the optical member according to claim 11.   An illumination device comprising the semiconductor light emitting device according to claim 13.   An image display device comprising the semiconductor light emitting device according to claim 13.