JP2019108528A - Curable organopolysiloxane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable organosilicon resin composition having excellent transparency, curability, heat resistance and light resistance, and a semiconductor device sealed with the composition. A curable organopolysiloxane composition comprising the following components (A) and (B). (A) The following formula (1) (in the above formula, R1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R2 is a divalent group having 6 to 50 carbon atoms which may have a silylene group or a siloxane bond. It is an organopolysiloxane having a siloxane unit represented by (which is an aromatic group), has a weight average molecular weight of 2,000 to 100,000, and has a weight average molecular weight (Mw) / number average molecular weight (Mn). The organopolysiloxane and (B) a basic catalyst, characterized in that the ratio is 1.5 or more. [Selection diagram] None

Description

  The present invention relates to a curable organopolysiloxane composition and a semiconductor device sealed with a cured product of the composition.

  To date, condensation curable organopolysiloxanes are widely used in applications such as adhesives, waterproof and moisture-proof coatings, electrical insulation films, and construction sealants. Moreover, in recent years, utilization as a sealing material of a photodiode (LED) attracts attention from the viewpoint of the high heat resistance, light resistance, etc. However, condensation-curable organopolysiloxanes have lower reactivity and poor productivity than addition-curable organopolysiloxanes. In addition, when a large amount of condensation catalyst is used to improve the reactivity, the deterioration of the silicone resin is also accelerated, so there is a problem that the high heat resistance and light resistance inherent to the silicone resin can not be exhibited. In addition, since the condensation catalyst itself is colored or becomes colored due to deterioration, many condensation catalysts are not suitable in the field where the heat resistance of the cured product is important.

  Various attempts have been made to improve and put to practical use of condensation curable organopolysiloxanes. For example, in Patent Document 1, an organopolysiloxane having two or more silanol groups in one molecule and an organopolysiloxane having two or more silicon-bonded alkoxy groups in one molecule are added to the metal catalyst of aluminum or zinc, and phosphorus. While attempting to improve the curing rate by adding a condensation catalyst of an acid ester or a boron compound, the resin deterioration is to be minimized. In addition, as in Patent Document 2, a cured product is obtained by adding a volatile amine catalyst to a partial hydrolyzate of tetraalkoxysilane or trialkoxysilane and a linear organopolysiloxane having both terminal silanol groups and curing the same. Attempts have also been made to reduce the amount of catalyst remaining in water. Furthermore, as in Patent Document 3, an attempt is also made to achieve gelation with a small number of reactions by previously polymerizing the condensable organopolysiloxane.

  However, the condensation-curable organosilicon resin composition described in the above-mentioned patent documents has not yet been satisfactory for applications in fields requiring high heat resistance and light resistance of the cured product. For example, the curable organosilicon resin composition described in Patent Document 1 is poor in heat resistance and light resistance because a large amount of catalyst is present in the cured product, and an excessive alkoxy group is contained in the composition. Therefore, during curing, a gas is generated by reaction byproducts, which causes a void. The resin composition of Patent Document 2 has a large change in viscosity because the amine catalyst exhibits a condensation action even at low temperatures, and has problems with storage stability and handling. In the case of a thick cured product, there is a problem that the amine catalyst is not sufficiently volatilized, the remaining amine catalyst is deteriorated by heat, and the cured product is discolored to brown. In the composition described in Patent Document 3, since the condensable polyorganosiloxane is made to have a high molecular weight, the viscosity of the composition becomes high, so it is not suitable for use in which the composition is poured into a recess and then cured.

JP, 2011-219729, A JP, 2016-8246, A JP, 2007-119569, A

  An object of the present invention is to provide a curable organosilicon resin composition excellent in transparency, curability, heat resistance and light resistance, in view of the above-mentioned circumstances. Another object of the present invention is to provide a semiconductor device in which a semiconductor element is sealed with the composition.

で示されるシロキサン単位を特定量含み、且つ特定の分子量分布を有する硬化性オルガノポリシロキサンと塩基性触媒とを含む硬化性オルガノポリシロキサン組成物が、優れた硬化性を有し、且つ高い耐熱性及び耐光性を有する硬化物を与えることができることを見出し、本発明を成すに至った。 MEANS TO SOLVE THE PROBLEM This inventor earnestly studies in order to solve the said subject, and following formula (1)

A curable organopolysiloxane composition containing a specific amount of a siloxane unit represented by and containing a curable organopolysiloxane having a specific molecular weight distribution and a basic catalyst has excellent curability and high heat resistance. It has been found that a cured product having light resistance can be provided, and the present invention has been achieved.

（上記式中、Ｒ^１は互いに独立に、炭素数１〜１０の１価炭化水素基であり、Ｒ^２は、シリレン基またはシロキサン結合を有してよい炭素数６〜５０の２価芳香族基である）
で示されるシロキサン単位を、全シロキサン単位の合計１００ｍｏｌ％に対して１０ｍｏｌ％以上で有し、且つ、Ｒ^１ＳｉＯ_３／２単位を１０〜９０ｍｏｌ％で有するオルガノポリシロキサンであって、
ゲルパーミエーションクロマトグラフィー（GPC）測定による標準ポリスチレン換算の重量平均分子量２，０００〜１００，０００を有し、且つ、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）の比が１．５以上であることを特徴とする、前記オルガノポリシロキサン、及び
（Ｂ）塩基性触媒 触媒量。
更に本発明は、該硬化性オルガノポリシロキサン組成物の硬化物を備える半導体装置を提供する。 That is, the present invention provides a curable organopolysiloxane composition comprising the following components (A) and (B).
(A) the following formula (1)

(Wherein, R ¹ is, independently of ^one another, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² is a divalent aromatic hydrocarbon having 6 to 50 carbon atoms that may have a silylene group or a siloxane bond Is the group)
Or a polysiloxane unit having 10 mol% or more based on 100 mol% of the total siloxane units, and having 10 to 90 mol% of R ¹ SiO _3/2 units,
It has a standard polystyrene equivalent weight average molecular weight of 2,000 to 100,000 as measured by gel permeation chromatography (GPC), and the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.5 or more Said organopolysiloxane, and (B) a basic catalyst a catalytic amount.
Furthermore, the present invention provides a semiconductor device provided with a cured product of the curable organopolysiloxane composition.

  The curable organopolysiloxane composition of the present invention has excellent curability and can give a cured product having excellent heat resistance and light resistance.

で示されるシロキサン単位を、全シロキサン単位の合計１００ｍｏｌ％に対して１０ｍｏｌ％以上で有し、且つ、Ｒ^１ＳｉＯ_３／２単位を１０〜９０ｍｏｌ％で有する。また、任意でＳｉＯ_４／２単位を０〜５０ｍｏｌ％、（Ｒ^１）_２ＳｉＯ_２／２単位を０〜７０ｍｏｌ％、並びに（Ｒ^１）_３ＳｉＯ_１／２単位を０〜３０ｍｏｌ％で有する。
なお、該オルガノポリシロキサンの構造は特に制限されるものでないが、好ましくはラダー構造またはレジン構造（三次元架橋構造）を有し、特に好ましくはレジン構造を有するオルガノポリシロキサンが良い。 Hereinafter, the present invention will be described in detail.
[(A) Curable organopolysiloxane]
(A) The curable organopolysiloxane has the following formula (1)

And 10 mol% or more based on 100 mol% in total of all the siloxane units, and 10 to 90 mol% of R ¹ SiO _3/2 units. In addition, it optionally has 0 to 50 mol% of SiO _4/2 units, 0 to 70 mol% of (R ¹ ) ₂ SiO _2/2 units, and 0 to 30 mol% of (R ¹ ) ₃ SiO _1/2 units.
The structure of the organopolysiloxane is not particularly limited, but it is preferably an organopolysiloxane having a ladder structure or a resin structure (three-dimensional crosslinked structure), and particularly preferably a resin structure.

The amount of the siloxane unit represented by the above formula (1) is 10 mol% or more, preferably 10 to 90 mol%, with respect to the total number of moles of all the siloxane units of the component (A) (total 100 mol%). More preferably, it is 20-80 mol%. In the above formulas, R ¹ is, independently of one another, a monovalent hydrocarbon group having 1 to 10, preferably 1 to 6, carbon atoms, and R ² may have a silylene group or a siloxane bond, having 6 carbon atoms And 50 divalent aromatic groups.

R ¹ represents an alkyl group such as methyl group, ethyl group, propyl group or butyl group; a cycloalkyl group such as cyclohexyl group; an aryl group such as phenyl group, tolyl group or xylyl group; an aralkyl group such as benzyl group; Groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, alkenyl groups such as octenyl groups, etc., and part or all of the above hydrocarbon groups are substituted with halogen atoms or the like. May be Among the above, a methyl group and a phenyl group are preferable.

（上記式中、Ｒ^１は前記と同じ）
で示されるようなケイ素原子を含むシリレン基またはシロキサン結合を有する基が例示される。中でも、シリレン基が好ましい。 R ² is a phenylene group, an arylene group such as a biphenylene group, an alkylarylene group, a diorganosilylene group such as a dimethylsilylene group, or a group having a siloxane bond represented by (R ¹ ) ₂ SiO _2/2 unit (R ¹ is as described above, and the following formula

(In the above formula, R ¹ is the same as above)
Examples thereof include a silylene group containing a silicon atom as shown in and a group having a siloxane bond. Among them, a silylene group is preferable.

  Also, the organopolysiloxane has a weight average molecular weight of 2,000 to 100,000, preferably 3,000 to 50,000. If the molecular weight is less than the above lower limit, the composition obtained may not be cured. If the molecular weight exceeds the above upper limit, the pot life of the composition may be deteriorated.

  The organopolysiloxane is characterized in that the value of the ratio (Mw / Mn) of weight average molecular weight Mw to number average molecular weight Mn is 1.5 or more. Preferably, it is Mw / Mn = 1.6-2.5. The polysiloxane having Mw / Mn less than the above-mentioned value is undergoing intramolecular condensation at the synthesis stage of the polysiloxane and has a stable cage structure. Since the polysiloxane having such a stable cage structure is unlikely to cause further polymerization, the curability of the resulting composition is deteriorated. On the other hand, the organopolysiloxane having Mw / Mn of 1.5 or more has an active reaction point, so that the reaction between molecules proceeds by the later-described basic catalyst, and it can be cured immediately.

In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are weight average molecular weights using polystyrene as a standard substance by gel permeation chromatography (GPC) measured under the following conditions.
[Measurement condition]
Developing solvent: Tetrahydrofuran (THF)
Flow rate: 0.6 mL / min
Detector: Differential Refractive Index Detector (RI)
Column: TSK Guardcolumn SuperH-L
TSKgel SuperH4000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H 3000 (6.0 mm ID × 15 cm × 1)
TSKgel Super H 2000 (6.0 mm ID × 15 cm × 2)
(All are made by Tosoh Corporation)
Column temperature: 40 ° C
Sample injection volume: 20 μL (THF solution with a concentration of 0.5% by weight)

  The organopolysiloxane having the above molecular weight distribution preferably has two or more, preferably two to five maximum values in a molecular weight distribution curve obtained by GPC measurement, and at least one maximum value has a molecular weight of 5,000. The above, preferably between 5,500 and 50,000, and at least one local maximum should be between molecular weight Mw 3,000 or less, preferably between 1,600 and 2,800. Furthermore, in the molecular weight distribution curve of the (A) organopolysiloxane, the area of a peak having a maximum at a position of a molecular weight of 5,000 or more (referred to as a peak on the high molecular weight side) and a position of a molecular weight of 3,000 or less The ratio to the area of the peak having the maximum value (referred to as the peak on the low molecular weight side) is 5:95 to 90:10, preferably 20:80 to 70:30. However, when the peak on the high molecular weight side and the peak on the low molecular weight side are adjacently overlapped, the valley between the two peaks (the point where the value is the minimum (point of the minimum value)) is the base The above ratio is calculated with the area divided by the perpendicular drawn to the line. If the molecular weight distribution does not satisfy the above, the curability of the resulting composition may be degraded.

  The molecular weight distribution curve may have a peak having a maximum value between 3,000 and 5,000. In the case where there are three or more maximum values, the maximum value having the largest molecular weight may be 5,000 or more, and the maximum value having the smallest molecular weight may be 3,000 or less. In the case where there is a peak having a maximum value between 3,000 and 5,000, and the weight average molecular weight determined together with the peak on the high molecular weight side is 5,000 or more, the peak The area can be added to the peak area as a high molecular weight peak.

The component (A) has an alkoxy group bonded to a silicon atom in an amount ranging from 0.001 to 2 mol / 100 g, and a hydroxyl group bonded to a silicon atom ranging from 0 mol / 100 g to 1.0 mol / 100 g In quantity. The amount of hydroxyl groups and the amount of alkoxy groups bonded to silicon atoms in the present invention are values measured by ¹ H-NMR and ²⁹ Si-NMR.

  The amount of the hydroxyl group bonded to the silicon atom is preferably 0.8 mol / 100 g or less, more preferably 0.1 mol / 100 g or less. The lower limit value of the hydroxyl group is not particularly limited and may be 0 mol / 100 g, preferably 0.0001 mol / 100 g or more. If the amount of hydroxyl groups bonded to silicon atoms exceeds the above upper limit value, voids may occur during curing.

  The amount of the alkoxy group bonded to the silicon atom is preferably 0.02 to 1.5 mol / 100 g, more preferably 0.6 mol / 100 g or less. If the amount of the alkoxy group bonded to the silicon atom exceeds the above upper limit value, there is a possibility that a void may be generated at the time of curing. Moreover, if it is less than the said lower limit, there exists a possibility that the adhesiveness of a base material and hardened | cured material may fall.

  The nature of the organopolysiloxane may be solid, semi-solid or liquid at 25 ° C.

The organopolysiloxane of the present invention essentially has an R ¹ SiO _3/2 unit in addition to the structure represented by the above formula (1). The number of R ¹ SiO _3/2 units (T units) is 10 to 90 mol%, preferably 10 to 80 mol%, more preferably the total number of moles of all siloxane units of the component (A) (total 100 mol%) Is 30 to 80 mol%. If it does not have a T unit, the curability of the composition may be poor. It also optionally has SiO _4/2 units, (R ¹ ) ₂ SiO _{2 2/2} units, or (R ¹ ) ₃ SiO _1/2 units (R ¹ is as described above). The content ratio of the unit may be 0 to 20 mol%, preferably 0 to 10 mol%, of the number of SiO _4/2 units (Q units). The number of (R ¹ ) ₂ SiO _2/2 units (D units) may be 0 to 70 mol%, preferably 0 to 50 mol%, and the number of (R ¹ ) ₃ SiO _1/2 units (M units) may be 0 to 30 mol%, preferably 0 to 20 mol%, more preferably 0 mol%.

  The organopolysiloxane of the present invention can be produced by dehydrogenation reaction, condensation reaction, or equilibration reaction of the above-mentioned organosilicon compounds as the source of each siloxane unit. The production method may be according to a conventionally known method, and a basic catalyst and an acidic catalyst can be mentioned as a reaction catalyst, but it is preferable to use an acidic catalyst in order to obtain an organopolysiloxane having the above-mentioned molecular weight distribution. When a basic catalyst is used, intramolecular condensation proceeds sufficiently in the synthesis stage of the siloxane, and the organopolysiloxane has a stable cage structure. Such an organopolysiloxane has a ratio (Mw / Mn) of weight average molecular weight Mw to number average molecular weight Mn of 1.5 or less. Further, as described above, since the polysiloxane having a stable cage structure is less likely to cause further polymerization, the curability of the resulting composition may be deteriorated.

As a material for obtaining R ¹ SiO _3/2 unit (T unit), for example, organotrichlorosilane represented by the following structural formula, organosilicon compounds such as organotrialkoxysilane, or condensation products thereof, or Examples include, but are not limited to, organosilicon compounds containing HSiO _2/2 units that can be dehydrogenated by boron catalysts.

（上記式中、ｎは０〜１００の整数、ｍは０〜１００の整数である。）

As a material for obtaining R ¹ ₂ SiO _2/2 units (D units), e.g., diorganodichlorosilane represented by the following structural formula, and organic silicon compounds such as diorganodialkoxysilanes are mentioned, these It is not limited to.

(In the above formula, n is an integer of 0 to 100 and m is an integer of 0 to 100.)

ＳｉＯ_４／２単位を得るための材料としては、例えば、ケイ酸ソーダ、テトラアルコキシシラン、またはその縮合反応物が例示できるが、これらに限定されるものではない。 As a material for obtaining the R ¹ ₃ SiO _1/2 units (M units), for example, triorganochlorosilane represented by the following structural formula, tri organoalkoxysilane, organosilicon compounds such as hexaorganodisiloxanes is However, it is not limited to these.

As a material for obtaining a SiO _4/2 unit, for example, sodium silicate, tetraalkoxysilane, or a condensation reaction product thereof can be exemplified, but it is not limited thereto.

Examples of the material for obtaining the unit represented by the formula (1) include, but are not limited to, organic silicon compounds such as 1,4-bis (dimethylsilyl) benzene represented by the following structural formula.

[(B) basic catalyst]
The component (B) is a basic catalyst and functions to promote the condensation reaction or the equilibrium polymerization reaction of the organopolysiloxane at the hydroxyl group bonded to the silicon atom of the organopolysiloxane. The basic catalyst may be any conventionally known catalyst used for the condensation reaction of siloxanes.

  Examples of the basic catalyst include amine compounds and metal compounds such as silicates, zirconium, titanium, tin, lithium, barium, zinc and iron. Examples of amine compounds include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, t-butylamine, n-pentylamine, neopentylamine, n-hexylamine, cyclopropylamine, and Primary alkylamines such as cyclohexylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, diisopropylethylamine, di-n-butylamine, methylethylamine, methylpropylamine, ethylpropylamine, methylisobutylamine, diisobutylamine , Di-t-butylamine, and secondary alkylamines such as methyl pentylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, N-ethyl dipene Tertiary alkylamines such as pyramine, tributylamine and trihexylamine, silazane, polysilazane and the like are mentioned. Examples of the metal compound include lead, tin, zinc, iron, zirconium, titanium, cerium, calcium and barium alkoxide or Carboxylic acid complexes such as barium diisopropoxy, lithium silicate, sodium silicate, alkali metal silicates such as potassium silicate, etc. may be mentioned. Among them, amine compounds such as di-n-butylamine, N-ethyldipropylamine, tri-n-butylamine, silazane, polysilazane, etc., alkoxides or carboxylic acid complexes of tin, zinc, zirconium, calcium, lithium silicate, silica Preferred are metal compounds such as acid sodium salts and alkali metal silicates such as potassium silicates.

  The amount of basic catalyst may be a catalytic amount for advancing the reaction. For example, it is preferable that it is 0.001-5 mass parts with respect to 100 mass parts of (A) component, and it is more preferable that it is 0.005-3 mass parts. If the amount of the catalyst is too large, the resulting cured product may be inferior in heat resistance and light resistance.

[(C) linear organopolysiloxane]
The curable organopolysiloxane composition of the present invention may further contain a linear organopolysiloxane as component (C). The amount of the component (C) is preferably 50 parts by mass or less, preferably 1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the component (A).

（式中、ｋは１〜１０，０００の整数であり、Ｒ^３は互いに独立に、炭素数１〜１０の１価炭化水素基であり、Ｒ^４は互いに独立に、水酸基、炭素数１〜１０のアルコキシ基、炭素数１〜１０の１価炭化水素基から選ばれる基または水素原子である） Component (C) is preferably a diorganopolysiloxane having silanol groups at both ends. The linear organopolysiloxane is preferably represented by the following formula (2).

(Wherein k is an integer of 1 to 10,000, R ³ independently of each other is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is independently of each other, a hydroxyl group, 1 to carbon atoms A group selected from an alkoxy group of 10, a monovalent hydrocarbon group of 1 to 10 carbon atoms, or a hydrogen atom)

In said formula, R < ³ > is mutually independently a C1-C10 monovalent hydrocarbon group. For example, saturated aliphatic hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group, alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group, vinyl group, allyl group, 5-hexenyl Groups, and unsaturated aliphatic hydrocarbon groups such as 9-decenyl group, aryl groups such as phenyl group and tolyl group, aromatic hydrocarbon groups such as aralkyl group such as benzyl group, phenylethyl group and phenylpropyl group, Some or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine, for example, halogenated monovalent hydrocarbon groups such as trifluoropropyl and chloropropyl Etc. Among these, C1-C5 saturated hydrocarbon groups, such as a methyl group, an ethyl group, and a propyl group, and a phenyl group are preferable. In addition to the substituents mentioned for R ³ , R ⁴ may, for example, be a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, an isopropoxy group or a butoxy group. Among these, a hydroxyl group, a methoxy group, a methyl group and a phenyl group are preferable.

（式中、ｓ、ｔ、ｕは０〜１０，０００の整数であり、ただしｓ＋ｔ＋ｕは１〜１０，０００である） Examples of the component (C) include organopolysiloxanes represented by the following formula.

(In the formula, s, t and u are integers from 0 to 10,000, provided that s + t + u is 1 to 10,000)

（式中、Ｒ^５は、互いに独立に、炭素数１〜１０の１価脂肪族炭化水素基であり、Ｒ^６は、互いに独立に、炭素数６〜１０の１価芳香族炭化水素基であり、ｐ、ｑ、及びｒは、互いに独立に０〜４の整数であり、但し、ｐ＋ｑ＋ｒ＝３又は４である） [(D) cyclic organopolysiloxane]
The curable organopolysiloxane composition of the present invention may further contain (D) a cyclic organopolysiloxane. The organopolysiloxane is preferably an organosilicon compound represented by the following formula (3).

(Wherein R ⁵ is, independently of each other, a C 1-10 monovalent aliphatic hydrocarbon group, and R ⁶ is, independently of each other, a C 6-10 monovalent aromatic hydrocarbon group And p, q and r each independently represent an integer of 0 to 4, provided that p + q + r = 3 or 4)

（ここでｐ、ｑ、ｒは上記の通りである） Preferably, a cyclic organopolysiloxane represented by the following formula (4) is preferable.

(Where p, q, r are as above)

  The above cyclic organopolysiloxane is liquid or solid at normal temperature, but it is reacted with the amine compound described in the above basic catalyst or a metal compound such as zirconium, titanium, tin, zinc and iron even when the compound is solid. Thus, it is possible to easily ring-open to obtain a liquid ring-opening polymer. In addition, since the cyclic organopolysiloxane represented by the formula (3) is mixed with the component (A) and then heated and mixed at a temperature of 50 ° C. to 200 ° C., it can be easily mixed. .

  It is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of (A) component, and, as for the quantity of cyclic organopolysiloxane, it is more preferable that it is 0.2-20 mass parts.

[(E) Phosphor]
The curable organopolysiloxane composition of the present invention may further contain (E) a phosphor. Since the curable organopolysiloxane composition of the present invention is excellent in heat resistance and light resistance, even when it contains a phosphor, there is no fear that the fluorescence characteristics will be significantly reduced as in the prior art.

  The phosphor is not particularly limited, and conventionally known phosphors may be used. For example, it is preferable to absorb light from a semiconductor element, particularly a semiconductor light emitting diode having a nitride-based semiconductor as a light emitting layer, and to convert the wavelength into light of a different wavelength. As such phosphors, for example, nitride-based phosphors / oxynitride-based phosphors mainly activated with lanthanide-based elements such as Eu and Ce, lanthanoids such as Eu, transition metals such as Mn, etc. Alkaline earth metal halogenapatite phosphors, alkaline earth metal borate halogen phosphors, alkaline earth metal aluminate phosphors, alkaline earth metal silicate phosphors, alkaline earth metals mainly activated by elements Sulfide phosphor, alkaline earth metal thiogallate phosphor, alkaline earth metal silicon nitride phosphor, germanate phosphor, or rare earth aluminate phosphor mainly activated with lanthanoid elements such as Ce, rare earth phosphor Silicate phosphors or organic and organic complex phosphors mainly activated by lanthanoid elements such as Eu, Ca-Al-Si-O-N oxynitride glass phosphors It is preferably at least one member selected from.

  The phosphor preferably has an average particle diameter of 10 nm or more, more preferably 10 nm to 10 μm, still more preferably 10 nm to 1 μm. The average particle size is measured by particle size distribution measurement by a laser light diffraction method such as a Cirrus laser measurement apparatus. The blending amount of the phosphor is preferably 0.1 to 2,000 parts by mass, more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of components other than the phosphor, for example, the component (A).

Other Components In addition to the components (A) to (E) described above, an adhesive agent and other additives may be added to the curable organopolysiloxane composition of the present invention as required.

  The adhesion promoter may be any known one, for example, phenyltrimethoxysilane, trimethoxysilane, triethoxysilane, methyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacrylic acid Roxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysila , N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-cyanopropyltriethoxysilane Examples thereof include ethoxysilane and oligomers thereof. In addition, these adhesion imparting agents can be mix | blended individually by 1 type or in combination of 2 or more types. The amount of the adhesion promoter is preferably 0.01 to 10 parts by mass, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the component (A).

Other additives include, for example, reinforcing inorganic fillers such as silica, glass fiber, fumed silica, etc., calcium carbonate, calcium silicate, titanium dioxide, ferric oxide, carbon black, zinc oxide, etc. Inorganic filler, silicon dioxide (silica: SiO ₂ ), zirconium oxide (zirconia: ZrO ₂ ), titanium oxide (TiO ₂ ), aluminum oxide (alumina: Al ₂ O ₃ ), zinc oxide (ZnO), iron oxide (Fe) ₂ O ₃ ), triiron tetraoxide (Fe ₃ O ₄ ), lead oxide (PbO ₂ ), tin oxide (SnO ₂ ), cerium oxide (Ce ₂ O _3, CeO ₂ ), calcium oxide (CaO), tetraoxide Examples include nanofillers such as trimanganese (Mn ₃ O ₄ ), magnesium oxide (MgO), and barium oxide (BaO). The amount of the additive may be appropriately adjusted within the range that does not impair the effect of the present invention. For example, the amount can be 600 parts by mass or less, preferably 1 to 600 parts by mass, more preferably 10 to 400 parts by mass, with respect to 100 parts by mass of the component (A).

  The curable organopolysiloxane composition of the present invention is liquid or solid at normal temperature (25 ° C.). The curable organopolysiloxane composition of the present invention cures sufficiently even at normal temperature (25 ° C.), but may be cured by heating as required. The temperature for heating can be, for example, 60 to 200 ° C. Depending on the application, it can be cured after being applied to a predetermined substrate.

  In the curable organopolysiloxane composition of the present invention, the time for the composition which is liquid at 150 ° C. to gelate is preferably less than 300 seconds, and more preferably 30 to 240 seconds. If the gelation time is less than 300 seconds, the curability is excellent and it is suitable as a molding material for compression molding or transfer molding. In the present invention, "gelation" refers to a state which is not solid but does not have fluidity, and "time to gelation" refers to the time until the liquid composition loses fluidity. It's time. Moreover, although the resin composition of this invention is liquid or solid at normal temperature as mentioned above, the composition of a solid also becomes liquid at 150 degreeC. Therefore, in the composition which is solid at room temperature, “the time until the composition which is liquid at 150 ° C. becomes gelled” is the time to gelation (loss of fluidity) once it becomes liquid at 150 ° C. I mean time. When gelation does not occur at 150 ° C. for 300 seconds, or when gelation is insufficient, the resin strength becomes extremely weak under molding conditions, and stress is received from the mold when it is removed from the mold after molding is finished. There is a risk of tearing. A composition which gelates at 150 ° C. for 300 seconds is preferable because it can have an appropriate resin strength under molding conditions and can withstand stress released from the mold.

  Moreover, 10 weight% or less is preferable and, as for the volatile component amount in 150 degreeC * 1 hour of the said resin composition, 0.01-5 weight% is more preferable. If the amount of volatile component is 10% by weight or less, voids are not generated at the time of curing, and curing shrinkage is also suppressed, which is preferable. The volatile component amount (%) is the weight reduction rate (%) of the composition after heating relative to the weight of the composition before heating.

  The curable organopolysiloxane composition of the present invention gives a cured product excellent in mechanical properties, crack resistance and heat resistance. Preferably, when the curable organopolysiloxane composition of the present invention is cured into a cured product having a thickness of 1 mm, the total light transmittance at a wavelength of 400 to 800 nm, in particular, the light transmittance at a wavelength of 450 nm is 70% or more It is preferable to have 80% or more. In the present invention, the total light transmittance is a value measured by the method described in JIS K 7361-1: 1999, and the light transmittance at 450 nm is the spectrophotometer manufactured by Hitachi, using the method of the above standard. It is a value measured using U-4100.

  In addition, the curable organopolysiloxane composition of the present invention can give a cured product having a refractive index of 1.40 to 1.70, preferably 1.45 to 1.56. The refractive index in the present invention is a refractive index at 25 ° C. measured in accordance with JIS K 7142: 2008, and can be measured by an Abbe refractometer.

  The cured product having the above-described transmittance and refractive index is excellent in transparency, and thus can be particularly suitably used for optical applications such as a sealing material of an LED.

<Semiconductor device>
The present invention also provides a semiconductor device in which a semiconductor element is sealed with a cured product obtained by curing the above curable organopolysiloxane composition.

  As described above, the cured product obtained from the curable organopolysiloxane composition of the present invention is excellent in transparency and heat resistance. Therefore, it is suitable as a lens material for a light emitting semiconductor device, a protective coating agent, a molding agent, etc., and is particularly useful for sealing LED elements such as blue LEDs, white LEDs, ultraviolet LEDs and the like. In addition, since the curable organopolysiloxane composition of the present invention is excellent in heat resistance, it can be used as a wavelength conversion film material by adding a silicate-based phosphor or a quantum dot phosphor to a long time under high humidity. It is possible to provide a light emitting semiconductor device which can ensure reliability, and is excellent in moisture resistance and long-term color rendering.

  In the case of sealing a light emitting semiconductor element such as an LED with the curable organopolysiloxane composition of the present invention, the curable organopolysiloxane composition of the present invention is formed on the LED element mounted on a pre-mold package made of thermoplastic resin. By applying a substance and curing the composition on the LED element, the LED element can be sealed with the cured product of the curable organopolysiloxane composition. Moreover, it can apply | coat on a LED element in the state of the varnish prepared by dissolving a composition in organic solvents, such as toluene and xylene. The amount of the organic solvent may be appropriately adjusted according to a conventionally known production method.

  The curable organopolysiloxane composition of the present invention can be used as a display material, an optical recording medium material, an optical device material, an optical material, or the like because of its properties such as excellent transparency, heat resistance, UV resistance, crack resistance, long-term reliability and the like. It is an optimum material for optical applications such as component materials, optical fiber materials, organic materials with optical and electronic functional properties, and semiconductor integrated circuit peripheral materials.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples. In addition, a part shows a mass part and a viscosity is a value in 25 degreeC. In the following, Me represents a methyl group, Ph represents a phenyl group, and Mw represents a weight average molecular weight. The weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using polystyrene as a standard substance by gel permeation chromatography (GPC). The detailed conditions are as described above.

で示されるシロキサン単位２０ｍｏｌ％からなるラダー構造のフェニルメチルポリシロキサン（但し、該ポリシロキサンの全置換基の一部は水酸基又はアルコキシ基である。以下同様。）を１００部、及び（Ｂ）成分として、ケイ酸リチウムを（Ａ）成分１００部に対して１質量部となる量を混合することによって、硬化性オルガノポリシロキサン組成物１を得た。
上記オルガノポリシロキサン（Ａ）は重量平均分子量（Ｍｗ）５，４００を有し、重量平均分子量Ｍｗ／数平均分子量Ｍｎの比が１．７である。ケイ素原子に結合した水酸基量０．１ｍｏｌ／１００ｇ、及びメトキシ基量０．６ｍｏｌ／１００ｇである。また、ＧＰＣ測定にて得られた分子量分布曲線において２つの極大値を有するピークを有し、高分子量側にあるピーク極大値の分子量は９，９００であり、低分子量側にあるピーク極大値の分子量は１，６００であり、高分子量側に在るピークの面積と低分子量側にあるピークの面積比が４６：５４である。 Example 1
As the component (A), 50 mol% of PhSiO _3/2 units, 30 mol% of PhMeSiO _2/2 units, and the following formula (5)

100 parts of phenylmethylpolysiloxane having a ladder structure consisting of 20 mol% of siloxane units shown in the above (provided that part of all the substituents of the polysiloxane is a hydroxyl group or an alkoxy group, the same shall apply hereinafter), and (B) component Curable organopolysiloxane composition 1 was obtained by mixing lithium silicate in an amount of 1 part by mass with respect to 100 parts of component (A).
The organopolysiloxane (A) has a weight average molecular weight (Mw) of 5,400, and the ratio of weight average molecular weight Mw / number average molecular weight Mn is 1.7. The amount of hydroxyl groups bonded to silicon atoms is 0.1 mol / 100 g, and the amount of methoxy groups is 0.6 mol / 100 g. The molecular weight of the peak maximum at the high molecular weight side is 9,900, and the peak maximum at the low molecular weight side has peaks having two maxima in the molecular weight distribution curve obtained by GPC measurement. The molecular weight is 1,600, and the area ratio of the peak on the high molecular weight side to the peak on the low molecular weight side is 46: 54.

で示されるシロキサン単位１０ｍｏｌ％からなるレジン構造のフェニルメチルポリシロキサンに替えた他は、実施例１を繰り返して硬化性オルガノポリシロキサン組成物２を得た。
上記オルガノポリシロキサン（Ａ）は、重量平均分子量Ｍｗ＝２，０００を有し、重量平均分子量Ｍｗ／数平均分子量Ｍｎの比が１．５であり、ＧＰＣ測定にて得られた分子量分布曲線において２つの極大値を有するピークを有し、高分子量側にあるピーク極大値の分子量が５，４００であり、低分子量側にあるピーク極大値の分子量が１，３００であり、高分子量側に在るピークの面積と低分子量側に在るピークの面積の比が５：９５であり、ケイ素原子に結合した水酸基量０．０２ｍｏｌ／１００ｇ、メトキシ基量０．３ｍｏｌ／１００ｇ、イソプロポキシ基量０．０１ｍｏｌ／１００ｇである。 Example 2
Component (A) in Example 1 is 40 mol% of MeSiO _3/2 units, 40 mol% of PhSiO _3/2 units, 10 mol% of Ph ₂ SiO _2/2 units, and the following formula (5)

A curable organopolysiloxane composition 2 was obtained by repeating Example 1 except that it was changed to a phenylmethylpolysiloxane having a resin structure consisting of 10 mol% of siloxane units shown in the above.
The organopolysiloxane (A) has a weight average molecular weight Mw = 2,000, a ratio of weight average molecular weight Mw / number average molecular weight Mn is 1.5, and a molecular weight distribution curve obtained by GPC measurement It has a peak having two maximum values, the molecular weight of the peak maximum value on the high molecular weight side is 5,400, the molecular weight of the peak maximum value on the low molecular weight side is 1,300, and is present on the high molecular weight side The ratio of the area of the peak to the area of the peak at the low molecular weight side is 5:95, and the amount of hydroxyl groups bonded to silicon atoms is 0.02 mol / 100 g, the amount of methoxy groups 0.3 mol / 100 g, the amount of isopropoxy groups It is .01 mol / 100 g.

で示されるシロキサン単位７０ｍｏｌ％からなるラダー構造のフェニルメチルポリシロキサンを１００部及び（Ｂ）ジイソプロポキシバリウムを０．０５部を混合することによって、硬化性オルガノポリシロキサン組成物３を得た。
上記オルガノポリシロキサンは、重量平均分子量Ｍｗ＝９８，０００であり、重量平均分子量Ｍｗ／数平均分子量Ｍｎの比２．０を有する。ＧＰＣ測定にて得られた分子量分布曲線において３つの極大値を有するピークを有し、高分子量側にある二つのピークの極大値の分子量が順に２００,４００および８，７００であり、低分子量側にあるピーク極大値の分子量が１，６００であり、高分子量側に在るピークの面積と低分子量側に在るピークの面積の比が９０：１０であり、ケイ素原子に結合した水酸基量０．０２ｍｏｌ／１００ｇ、メトキシ基量０．３ｍｏｌ／１００ｇ、イソプロポキシ基量０．０１ｍｏｌ／１００ｇである。 [Example 3]
30 mol% of MeSiO _3/2 units and the following formula (5):

A curable organopolysiloxane composition 3 was obtained by mixing 100 parts of a phenylmethylpolysiloxane having a ladder structure consisting of 70 mol% of siloxane units shown by and a 0.05 part of (B) diisopropoxybarium.
The organopolysiloxane has a weight average molecular weight Mw of 98,000 and a weight average molecular weight Mw / number average molecular weight Mn ratio of 2.0. In the molecular weight distribution curve obtained by GPC measurement, it has peaks having three maxima, and the maxima of the two maxima on the high molecular weight side are 200, 400 and 8, 700 in order, and the low molecular weight side The peak maximum has a molecular weight of 1,600 and the ratio of the area of the peak on the high molecular weight side to the area of the peak on the low molecular weight side is 90:10, and the amount of hydroxyl groups bonded to silicon atoms is 0 .02 mol / 100 g, the amount of methoxy groups is 0.3 mol / 100 g, and the amount of isopropoxy groups is 0.01 mol / 100 g.

で示される直鎖状オルガノポリシロキサンを（Ａ）成分１００部に対して５０部となる量を添加した他は、実施例１を繰り返して、硬化性オルガノポリシロキサン組成物４を得た。 Example 4
In addition to the composition of Example 1, as the component (C), the following formula (6)

A curable organopolysiloxane composition 4 was obtained by repeating Example 1 except that 50 parts of the linear organopolysiloxane shown in the above was added with respect to 100 parts of the component (A).

で示される有機ケイ素化合物を（Ａ）成分１００部に対して２０部となる量添加した他は、実施例１を繰り返して硬化性オルガノポリシロキサン組成物５を得た。 [Example 5]
In addition to the composition of Example 1, as the component (D), the following formula (7)

A curable organopolysiloxane composition 5 was obtained by repeating Example 1 except that 20 parts of the organosilicon compound shown in the above were added with respect to 100 parts of the component (A).

で示されるシロキサン単位３０ｍｏｌ％からなるラダー構造のフェニルメチルポリシロキサンに替えた他は、実施例１を繰り返して硬化性オルガノポリシロキサン組成物６を得た。
上記フェニルメチルポリシロキサンは、重量平均分子量Ｍｗ＝９，５００を有し、重量平均分子量Ｍｗ／数平均分子量Ｍｎの比１．５を有する。さらに、分子量分布に２つの極大値を有し、高分子量側のピーク極大値の分子量が２０，２００であり、低分子量側のピーク極大値の分子量が２，６００であり、高分子量のものと低分子量のものの面積比が５０：５０であり、ケイ素原子に結合した水酸基量０．０１ｍｏｌ／１００ｇ、メトキシ基量０．０００５ｍｏｌ／１００ｇである。 [Example 6]
40 mol% of MeSiO _3/2 units, 30 mol% of PhSiO _3/2 units,
And the following formula (5)

A curable organopolysiloxane composition 6 was obtained by repeating Example 1 except that it was changed to a phenylmethylpolysiloxane having a ladder structure consisting of 30 mol% of siloxane units shown in the above.
The above phenylmethylpolysiloxane has a weight average molecular weight Mw = 9,500, and has a ratio of weight average molecular weight Mw / number average molecular weight Mn. Furthermore, the molecular weight distribution has two maximum values, the molecular weight of the peak maximum value on the high molecular weight side is 20,200, and the molecular weight of the peak maximum value on the low molecular weight side is 2,600, and those of high molecular weight The area ratio of low molecular weight ones is 50: 50, the amount of hydroxyl groups bonded to silicon atoms is 0.01 mol / 100 g, and the amount of methoxy groups is 0.0005 mol / 100 g.

Comparative Example 1
Except that the component (A) in Example 1 is replaced by a phenylmethylpolysiloxane having a resin structure consisting of 50 mol% of MeSiO _3/2 units, 20 mol% of PhSiO _3/2 units, and 30 mol% of Ph ₂ SiO _2/2 units. Example 1 was repeated to obtain a curable organopolysiloxane composition 7.
The above phenylmethylpolysiloxane has a weight average molecular weight Mw = 5,000, and has a ratio of weight average molecular weight Mw / number average molecular weight Mn of 1.5. In addition, the molecular weight distribution curve obtained by GPC measurement has peaks having two maximum values, and the peak maximum value at the high molecular weight side is 6,900, and the peak maximum value at the low molecular weight side is The molecular weight is 2,600, the ratio of the area of the peak on the high molecular weight side to the area of the peak on the low molecular weight side is 41:59, the amount of hydroxyl groups bonded to silicon atoms 0.9 mol / 100 g, methoxy Base amount 0.003 mol / 100 g.

で示されるシロキサン単位８ｍｏｌ％からなるレジン構造のフェニルメチルポリシロキサンに替えた他は、実施例１を繰り返して硬化性オルガノポリシロキサン組成物８を得た。
上記フェニルメチルポリシロキサンは、重量平均分子量Ｍｗ＝４，２００を有し、重量平均分子量Ｍｗ／数平均分子量Ｍｎの比１．５を有する。また、ＧＰＣ測定にて得られた分子量分布曲線において２つの極大値を有するピークを有し、高分子量側にあるピーク極大値の分子量が５，９００であり、低分子量側にあるピーク極大値の分子量が１，６００であり、高分子量側に在るピークの面積と低分子量側に在るピークの面積の比が５２：４８であり、ケイ素原子に結合した水酸基量０．１ｍｏｌ／１００ｇ、メトキシ基量１．６ｍｏｌ／１００ｇである。 Comparative Example 2
Component (A) in Example 1 is 92 mol% of PhSiO _3/2 unit,
And the following formula (5)

A curable organopolysiloxane composition 8 was obtained by repeating Example 1 except that it was changed to a phenylmethylpolysiloxane having a resin structure consisting of 8 mol% of siloxane units shown in the above.
The above phenylmethylpolysiloxane has a weight average molecular weight Mw = 4,200, and has a ratio of weight average molecular weight Mw / number average molecular weight Mn. In addition, the molecular weight distribution curve obtained by GPC measurement has peaks having two maximum values, and the peak maximum value at the high molecular weight side has a molecular weight of 5,900 and the peak maximum value at the low molecular weight side The molecular weight is 1,600, and the ratio of the area of the peak on the high molecular weight side to the area of the peak on the low molecular weight side is 52: 48, and the amount of hydroxyl groups bonded to silicon atoms is 0.1 mol / 100 g, methoxy The base weight is 1.6 mol / 100 g.

で示されるシロキサン単位５０ｍｏｌ％からなる直鎖状のフェニルメチルポリシロキサンに替えた他は、実施例１を繰り返して硬化性オルガノポリシロキサン組成物９を得た。
該フェニルメチルポリシロキサンは、重量平均分子量Ｍｗ＝１８，２００を有し、重量平均分子量Ｍｗ／数平均分子量Ｍｎの比１．３を有する。
また、ＧＰＣ測定にて得られた分子量分布曲線において１つの極大値を有するピークを有し、ケイ素原子に結合した水酸基量０．０１ｍｏｌ／１００ｇ、メトキシ基量０．０２ｍｏｌ／１００ｇである。 Comparative Example 3
Component (A) in Example 1 is 50 mol% of MePhSiO _2/2 unit,
And the following formula (5)

A curable organopolysiloxane composition 9 was obtained by repeating Example 1 except that it was changed to a linear phenylmethylpolysiloxane composed of 50 mol% of a siloxane unit shown in the above.
The phenylmethylpolysiloxane has a weight average molecular weight Mw = 18,200, and has a ratio of weight average molecular weight Mw / number average molecular weight Mn.
The molecular weight distribution curve obtained by GPC measurement has a peak having one maximum value, and the amount of hydroxyl groups bonded to a silicon atom is 0.01 mol / 100 g and the amount of methoxy groups is 0.02 mol / 100 g.

で示されるシロキサン単位２５ｍｏｌ％からなるレジン構造のフェニルメチルポリシロキサンに替えた他は、実施例１を繰り返して硬化性オルガノポリシロキサン組成物１０を得た。
該フェニルメチルポリシロキサンは、重量平均分子量Ｍｗ＝２，８００であり、重量平均分子量Ｍｗ／数平均分子量Ｍｎの比１．３を有する。
また、ＧＰＣ測定にて得られた分子量分布曲線において２つの極大値を有するピークを有し、Ｍｗが５，０００以上であるピークを有さず、２つの極大値の分子量は順に３，０００および１，６００であり、ケイ素原子に結合した水酸基量０．１ｍｏｌ／１００ｇ、メトキシ基量１．６ｍｏｌ／１００ｇである。 Comparative Example 4
Component (A) in Example 1 is 75 mol% of PhSiO _3/2 unit,
And the following formula (5)

A curable organopolysiloxane composition 10 was obtained by repeating Example 1 except that it was changed to a phenylmethylpolysiloxane having a resin structure consisting of 25 mol% of a siloxane unit shown in the above.
The phenylmethylpolysiloxane has a weight average molecular weight Mw = 2,800 and a weight average molecular weight Mw / number average molecular weight Mn ratio of 1.3.
Moreover, it has a peak which has two maximum values in the molecular weight distribution curve obtained by GPC measurement, does not have a peak whose Mw is 5,000 or more, and the molecular weight of two maximum values is 3,000 and in order The amount of hydroxyl groups bonded to silicon atoms is 0.1 mol / 100 g, and the amount of methoxy groups is 1.6 mol / 100 g.

The physical properties of the curable organopolysiloxane compositions 1 to 10 produced in the above Examples and Comparative Examples and the cured products obtained from the respective compositions were evaluated according to the following methods. The results are shown in Tables 1 and 2.
(1) Appearance The color and transparency of a cured product (thickness 1 mm) obtained by curing each composition at 150 ° C. for 4 hours were visually confirmed.
(2) Properties The flowability of each composition before curing was confirmed. 50 g of the composition was placed in a 100 ml glass bottle, and the glass bottle was turned sideways and allowed to stand at 25 ° C. for 10 minutes. During that time, it was judged to be liquid if the composition flowed out.
(3) Refractive index Based on JIS K 7142: 2008, the refractive index of a 0.5 mm thick cured product obtained by curing each composition at 150 ° C. for 4 hours according to JIS K 7142: 2008, Abbe type It was measured by a refractometer.

(4) Hardness (type D)
The hardness of the cured product obtained by curing each composition at 150 ° C. for 4 hours was measured using a durometer D hardness meter in accordance with JIS K 6249: 2003.
(5) Elongation at break and tensile strength The elongation at break and tensile strength of a cured product obtained by curing each composition at 150 ° C. for 4 hours were measured according to JIS K 6249: 2003.

(6) Heat resistance (light transmittance retention rate) and crack resistance The light transmittance at a wavelength of 450 nm of a cured product (thickness 1 mm) obtained by curing each composition at 150 ° C. for 4 hours was measured by Hitachi It measured at 23 degreeC using photometer U-4100 (initial stage transmittance). Next, the cured product was heat-treated at 250 ° C. for 1,000 hours, and then the light transmittance was similarly measured to determine the light transmittance after the heat treatment with respect to the initial transmittance (100%). Moreover, the presence or absence of the crack in the hardened | cured material after heat processing was confirmed visually, and the thing without a crack was made into * and the thing which the crack generate | occur | produced was made into x.

(7) Nonvolatile property 1.0g of each composition was added to the aluminum petri dish, and heat processing were performed on conditions of 150 degreeC 1 hour. The weight of the cured product after the heat treatment was measured, and the weight (%) after the heat treatment with respect to the weight (100%) before the heat treatment is described in Tables 1 and 2.

(8) Adhesiveness 0.25 g of each composition is formed on a silver-plated plate having an area of 180 mm ^{2 so} that the bottom area is 45 mm ² and cured at 150 ° C. for 4 hours, and then cured using a micro spatula Was broken and peeled off from the silver plate, the ratio of the cohesive failure part and the ratio of the peeled part were determined. The adhesion was judged based on the following criteria.
(Judgment criteria)
Cohesive failure rate is 80% or more: Good adhesion (○)
The percentage of cohesive failure is 50% or more and less than 80%: Adhesion is generally good (Δ)
The percentage of cohesive failure is less than 50%: poor adhesion (x)

(9) Adhesion of dust due to surface tackiness Each composition was cured at 150 ° C. for 4 hours, and the presence or absence of adhesion of dust on the surface of a cured product obtained was visually confirmed.

(10) Curability (gelation)
1.0 g of each composition was molded under the conditions of 150 ° C. × 300 seconds using a molding machine FFT-1030 manufactured by TOWA Co., Ltd., and it was confirmed whether a molded resin could be formed on a glass epoxy substrate under the above molding conditions . The formability was evaluated based on the following criteria.
(Judgment criteria)
:: Normal molding was possible without peeling or resin breakage (sufficiently gelled)
X: Peeling or resin breakage occurred (insufficient gelation)

As shown in Table _{^{2, -O 1/2 Si (R 1}} ) 2 -R 2 -Si (R 1) 2 O 1/2 - composition of Comparative Example 1 having no units represented by the resin strength It was inferior to hardenability, and cracks were generated during heat treatment, and there were also many volatile components. _{^{-O 1/2 Si (R 1) 2}} -R 2 -Si (R 1) 2 O 1/2 - composition of Comparative Example 2 in which the unit is below 10 mol% represented by the poor curability, heat treatment Crack occurred. A composition of Comparative Example 3 which contains an organopolysiloxane which does not contain R ¹ SiO _3/2 units and which has a weight average molecular weight Mw / number average molecular weight Mn of less than 1.5 in place of the component (A) is , The resin did not cure. The composition of Comparative Example 4 containing an organopolysiloxane having a weight-average molecular weight Mw / number-average molecular weight Mn of less than 1.5 instead of the component (A) cures slowly, and voids occur during curing. The resin became brittle.
On the other hand, as shown in Table 1, the curable organopolysiloxane composition of the present invention is colorless and transparent and is excellent in curability, and the cured product obtained from the composition has sufficient hardness and elongation at break, It has tensile strength, good refractive index, heat resistance, crack resistance, adhesion, and no dust adhesion due to surface tackiness.

  The curable organopolysiloxane composition of the present invention can be cured rapidly to give a cured product, and the resulting cured product has high transparency, heat resistance, mechanical properties, crack resistance, and adhesiveness. Can. Moreover, if it is a composition of this invention, the hardened | cured material in which surface tackiness was suppressed can be given. Therefore, it can be used suitably as a composition for semiconductor element closure, and a highly reliable semiconductor device can be provided.

Claims (9)

Curable organopolysiloxane composition (A) containing the following components (A) and (B):

(Wherein, R ¹ is, independently of ^one another, a monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ² is a divalent aromatic hydrocarbon having 6 to 50 carbon atoms that may have a silylene group or a siloxane bond Is the group)
Or a polysiloxane unit having 10 mol% or more based on 100 mol% of the total siloxane units, and having 10 to 90 mol% of R ¹ SiO _3/2 units,
It has a standard polystyrene equivalent weight average molecular weight of 2,000 to 100,000 as measured by gel permeation chromatography (GPC), and the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.5 or more Said organopolysiloxane, and (B) a basic catalyst a catalytic amount.   The component (A) has an alkoxy group bonded to a silicon atom in an amount ranging from 0.001 to 2 mol / 100 g, and a hydroxyl group bonded to a silicon atom ranging from 0 mol / 100 g to 1.0 mol / 100 g The curable organopolysiloxane composition of claim 1 having an amount. The curing according to claim 1 or 2, further comprising (C) a linear organopolysiloxane represented by the following formula (2) in an amount of 50 parts by mass or less based on 100 parts by mass of the component (A). Organopolysiloxane composition

(Wherein k is an integer of 1 to 10,000, R ³ independently of each other is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ is independently of each other, a hydroxyl group, 1 to carbon atoms A group selected from an alkoxy group of 10 and a monovalent hydrocarbon group of 1 to 10 carbon atoms, or a hydrogen atom). Furthermore (D) the following formula (3)

(Wherein R ⁵ is, independently of each other, a C 1-10 monovalent aliphatic hydrocarbon group, and R ⁶ is, independently of each other, a C 6-10 monovalent aromatic hydrocarbon group And p, q and r each independently represent an integer of 0 to 4, provided that p + q + r = 3 or 4)
The curable organopolysiloxane composition according to any one of claims 1 to 3, containing 0.1 to 30 parts by mass of the organosilicon compound represented by 100 parts by mass of the component (A).   The molecular weight distribution curve obtained by GPC measurement of the (A) organopolysiloxane has two or more maximum values, at least one maximum value has a molecular weight of 5,000 or more, and at least one maximum value has a molecular weight of 3 The curable organopolysiloxane composition according to any one of claims 1 to 4, wherein the amount is 1,000 or less.   In the molecular weight distribution curve of the (A) organopolysiloxane, the ratio of the area of the peak having a maximum at a position of a molecular weight of 5,000 or more to the area of the peak having a maximum at a position of a molecular weight of 3,000 or less is 5 : 95 to 90: 10 (however, when peaks overlap, it is the ratio of the area divided by the vertical line drawn from the point of the local minimum between the two peaks with respect to the baseline 6) The curable organopolysiloxane composition according to claim 5.   The curable organopolysiloxane composition according to any one of claims 1 to 6, wherein the time for the liquid composition to gel at 150 ° C is less than 300 seconds.   The curable organopolysiloxane composition according to any one of claims 1 to 7, wherein the weight loss rate at 150 ° C for one hour heating is 10% by weight or less based on the weight of the composition before heating.   A semiconductor device comprising a cured product obtained by curing the curable organopolysiloxane composition according to any one of claims 1 to 8.