WO2017056913A1 - Composition de résine de silicone durcissable, son produit durci, et dispositif semi-conducteur optique utilisant ledit produit durci - Google Patents

Composition de résine de silicone durcissable, son produit durci, et dispositif semi-conducteur optique utilisant ledit produit durci Download PDF

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WO2017056913A1
WO2017056913A1 PCT/JP2016/076543 JP2016076543W WO2017056913A1 WO 2017056913 A1 WO2017056913 A1 WO 2017056913A1 JP 2016076543 W JP2016076543 W JP 2016076543W WO 2017056913 A1 WO2017056913 A1 WO 2017056913A1
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general formula
carbon atoms
group
component
silicone resin
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PCT/JP2016/076543
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English (en)
Japanese (ja)
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佑 松野
勝宏 秋山
亘 河合
真 情野
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セントラル硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805—Shape
    • H01L2224/4809—Loop shape
    • H01L2224/48091—Arched

Definitions

  • the present invention relates to a curable silicone resin composition that can be suitably used as a sealing material for an optical semiconductor element or a raw material for an adhesive, a cured product thereof, and an optical semiconductor device using the same.
  • a cured product such as an epoxy resin composition or a silicone resin composition is used as a sealing material of a light emitting device using an optical semiconductor element such as a light emitting diode (abbreviation: LED).
  • LED light emitting diode
  • the epoxy resin composition has excellent handling properties because of the high hardness of the cured product.
  • the required durability can be obtained. Many are used.
  • the cured products of conventional transparent epoxy resin compositions have power semiconductors and high-intensity light emitting elements (for example, the backlights of automobile headlights and LCD TVs). It is known that heat resistance is insufficient for use as a sealing material for short-wavelength semiconductor lasers such as high-intensity LEDs for light or blue lasers, and current leakage or yellowing due to high-temperature deterioration occurs. .
  • Patent Document 1 reports an addition-curable silicone resin composition that uses an addition reaction (hydrosilylation reaction) between a Si—H group and an alkenyl group as a material for protecting and sealing an optical device or a semiconductor device. ing.
  • the silicone resin is inferior to the epoxy resin in mechanical properties and adhesiveness, only a sealing form in a gel state can be selected. Therefore, the problem that surface tack (stickiness) and deformation occur after sealing has been pointed out in the market.
  • the present invention has been made in view of the above circumstances, and is an addition-curable curable silicone resin composition that provides an encapsulant for optical semiconductor devices that does not contain bubbles and has no tackiness, and a cured product thereof, and It is an object to provide an optical semiconductor device using these.
  • the present inventors have intensively studied to achieve the above-mentioned problems. As a result, it has been found that the above-mentioned problems can be achieved by using a curable silicone resin composition containing at least a predetermined component, and has excellent defoaming properties and excellent surface tack suppression. It came to complete the addition-curable curable silicone resin composition which gives.
  • the present invention includes the following inventions.
  • a curable silicone resin composition comprising at least the following component (A), component (B) and component (C).
  • R 3 represents an aromatic hydrocarbon group having an aliphatic hydrocarbon group or a C 6-10 having 1 to 6 carbon atoms
  • R 4 represents an alkyl group having 1 to 3 carbon atoms
  • R 5 represents an alkyl group having 1 to 3 carbon atoms.
  • the molar ratio of the trialkoxysilane represented by the general formula [1] and the dialkoxysilane represented by the general formula [2] is 85:15 to 15:85,
  • the curable silicone resin according to the invention 1 or 2 wherein the compounding amount of the vinyltrialkoxysilane represented by [3] is 1 to 40 mol with respect to 100 mol of the total amount of the trialkoxysilane and the dialkoxysilane. Composition.
  • invention 4 The curable silicone resin according to any one of inventions 1 to 3, wherein the hydrolytic polycondensation of the first alkoxysilane composition is performed in the presence of a basic organic compound having a pKa (20 ° C, in water) of 9 or more. Composition.
  • composition according to any one of claims 1 to 5, wherein the component (B) is the following component (B-1).
  • Component (B-1) hydrolysis polycondensation of a second alkoxysilane composition containing at least a trialkoxysilane represented by the following general formula [5] and a dialkoxysilane represented by the general formula [6] And a hydrolysis polycondensation product having a HO—Si group obtained by the following formula and a silane compound represented by the following general formula [8-1], [8-2], [8-3] or [8-4]
  • a silicone resin having a Si—H group obtained by reacting at least one kind.
  • R 7 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • R 8 represents an alkyl group having 1 to 3 carbon atoms
  • R 9 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • R 10 represents an alkyl group having 1 to 3 carbon atoms.
  • R 12 represents an alkyl group having 1 to 3 carbon atoms
  • R 13 represents an alkyl group having 1 to 3 carbon atoms.
  • the molar ratio of the trialkoxysilane represented by the general formula [5] and the dialkoxysilane represented by the general formula [6] is 85:15 to 15:85
  • [Invention 10] The curable silicone resin composition according to any one of Inventions 1 to 5, wherein the component (B) is the following component (B-3).
  • R 14 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and two R 14 are the same or different from each other.
  • R 15 represents an alkyl group having 1 to 3 carbon atoms, and two R 15 may be the same or different from each other.
  • R 16 represents a fatty acid having 1 to 6 carbon atoms.
  • R 17 represents an alkyl group having 1 to 3 carbon atoms, and two R 17 may be the same or different from each other.
  • invention 11 Curing retarder, adhesion promoter, antioxidant, light stabilizer, phosphor, inorganic particles, mold release agent, resin modifier, colorant, diluent, antibacterial agent, antifungal agent, leveling agent and anti-sagging agent
  • curable silicone resin composition according to any one of inventions 1 to 10, further comprising at least one selected from the group consisting of:
  • An optical semiconductor device comprising at least an optical semiconductor element and the cured product according to the twelfth aspect of the invention provided to seal the optical semiconductor element.
  • a first alkoxysilane composition comprising at least a trialkoxysilane represented by the following general formula [1], a dialkoxysilane represented by the general formula [2], and a vinyltrialkoxysilane represented by the general formula [3]
  • R 3 represents an aromatic hydrocarbon group having an aliphatic hydrocarbon group or a C 6-10 having 1 to 6 carbon atoms
  • R 4 represents an alkyl group having 1 to 3 carbon atoms
  • R 5 represents an alkyl group having 1 to 3 carbon atoms.
  • a first alkoxysilane composition comprising at least a trialkoxysilane represented by the following general formula [1], a dialkoxysilane represented by the general formula [2], and a vinyltrialkoxysilane represented by the general formula [3]
  • a method for producing a first silicone resin having a mass average molecular weight of 3,800 to 20,000 by hydrolytic polycondensation In the general formula [1], R 1 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 2 represents an alkyl group having 1 to 3 carbon atoms.
  • R 3 represents an aromatic hydrocarbon group having an aliphatic hydrocarbon group or a C 6-10 having 1 to 6 carbon atoms
  • R 4 represents an alkyl group having 1 to 3 carbon atoms
  • R 5 represents an alkyl group having 1 to 3 carbon atoms.
  • the molar ratio of the trialkoxysilane represented by the general formula [1] and the dialkoxysilane represented by the general formula [2] is 85:15 to 15:85,
  • the method according to invention 16 or 17, wherein the compounding amount of the vinyltrialkoxysilane represented by [3] is 1 to 40 mol with respect to 100 mol of the total amount of the trialkoxysilane and dialkoxysilane.
  • [Invention 21] A method for producing a curable silicone resin composition by blending at least the following component (A), component (B) and component (C).
  • a first silicone resin having a mass average molecular weight of 3,800 to 20,000 obtained by hydrolytic polycondensation of the alkoxysilane composition of (In the general formula [1], R 1 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 2 represents an alkyl group having 1 to 3 carbon atoms.
  • R 3 represents an aromatic hydrocarbon group having an aliphatic hydrocarbon group or a C 6-10 having 1 to 6 carbon atoms
  • R 4 represents an alkyl group having 1 to 3 carbon atoms
  • R 5 represents an alkyl group having 1 to 3 carbon atoms.
  • [Invention 22] A method for producing a curable silicone resin composition by blending at least the following component (A), component (B) and component (C).
  • Component (A) a first containing at least a trialkoxysilane represented by the following general formula [1], a dialkoxysilane represented by the general formula [2], and a vinyltrialkoxysilane represented by the general formula [3] 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, guanidine, tetramethylguanidine, 7-methyl -1,5,7-triazabicyclo [4.4.0] -5-decene and at least one selected from the group consisting of 1,5,7-triazabicyclo [4.4.0] -5-decene
  • a first silicone resin having a mass average molecular weight of 3,800 to 20,000, obtained by hydrolytic polycondensation in the presence of a basic organic
  • R 1 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • R 2 represents an alkyl group having 1 to 3 carbon atoms
  • R 3 represents an aromatic hydrocarbon group having an aliphatic hydrocarbon group or a C 6-10 having 1 to 6 carbon atoms
  • R 4 represents an alkyl group having 1 to 3 carbon atoms
  • R 5 represents an alkyl group having 1 to 3 carbon atoms.
  • pKa means the logarithmic value of the reciprocal of the acid dissociation constant at 20 ° C. in water.
  • pKa is a value determined by a known titration method (a method for measuring an acid dissociation constant based on the Bronsted definition).
  • aliphatic hydrocarbon group having 1 to 6 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, isobutyl group, n- A pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group and the like can be mentioned.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted or unsubstituted, and part or all of the hydrogen atoms are fluorine atoms, alkyl groups having 1 to 3 carbon atoms, or carbon atoms. It may be substituted with 1 to 3 fluoroalkyl groups. Specific examples include phenyl group, naphthyl group, xylyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-ditrifluoromethylphenyl group, and the like.
  • alkyl group having 1 to 3 carbon atoms examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • fluoroalkyl group having 1 to 3 carbon atoms include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, perfluoropropyl group, 1,1,1,3 , 3,3-hexafluoroisopropyl group and the like.
  • a methyl group may be represented as Me
  • a phenyl group may be represented as Ph
  • a vinyl group (—CH ⁇ CH 2 group) may be represented as Vi.
  • the trialkoxysilane represented by the general formula [1] may be represented as “trialkoxysilane [1]”.
  • dialkoxysilane represented by the general formula [2], etc. May also be represented as “dialkoxysilane [2]” or the like.
  • the silane compound represented by the general formula [8-1] may be represented as “silane compound [8-1]”, and may be represented by the silane compound represented by [8-2] to [8-4].
  • the silane compounds represented may be represented as “silane compound [8-2]” to “silane compound [8-4]”, respectively. Compound [8] ".
  • component (B) items common to the component (B-1), the component (B-2), and the component (B-3) may be collectively referred to as “component (B)”.
  • an addition-curable curable silicone resin composition that does not contain bubbles and has no tackiness, and a cured product thereof, and an optical semiconductor device using them. Can be provided.
  • the curable silicone resin composition of the present invention (sometimes referred to simply as “the composition of the present invention” in the present specification) is a first silicone resin as component (A) and a second as component (B). And at least a hydrosilylation catalyst as component (C).
  • the composition of the present invention is suitably used for producing the optical semiconductor device of the present invention.
  • the composition of the present invention may further contain other components.
  • the component (A) includes at least a trialkoxysilane represented by the following general formula [1], a dialkoxysilane represented by the general formula [2], and a vinyltrialkoxysilane represented by the general formula [3].
  • 1 is a silicone resin (first silicone resin) having a mass average molecular weight of 3,800 to 20,000 obtained by hydrolytic polycondensation of one alkoxysilane composition.
  • R 1 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • R 2 represents an alkyl group having 1 to 3 carbon atoms, and the three R 2 may be the same or different from each other.
  • R 1 is a methyl group, an ethyl group, a phenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-di (trifluoromethylphenyl) group are preferable, and particularly preferably a phenyl group.
  • R 2 is preferably a methyl group or an ethyl group.
  • R 3 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the two R 3 may be the same or different from each other.
  • R 4 represents an alkyl group having 1 to 3 carbon atoms, two R 4 may be the same or different types from each other.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group, and particularly preferably a methyl group.
  • R 4 is preferably a methyl group or an ethyl group.
  • R 5 represents an alkyl group having 1 to 3 carbon atoms, the three R 5 may be the same or different types from each other.
  • R 5 is preferably a methyl group or an ethyl group.
  • trialkoxysilane [1] include, but are not limited to, the following compounds: methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltriisopropoxysilane, isopropyltrimethoxysilane , Isopropyltriethoxysilane, isopropyltripropoxysilane, isopropyltriisopropoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane,
  • preferred compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, 3 -(Trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane, 3, 5- (ditrifluoromethyl) phenyltriethoxysilane can be mentioned, and particularly preferred compounds include phenyltrimethoxysilane and phenyltriethoxysilane.
  • dialkoxysilane [2] include, but are not limited to, the following compounds: dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyl Diethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, di (n-propyl) dimethoxysilane, di (n-propyl) diethoxysilane, di (n-propyl) dipropoxysilane, di (n-propyl) Diisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, di (n-butyl) dimethoxysilane, di (n-butyl
  • preferred compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, di (3-trifluoromethylphenyl) dimethoxysilane, di (3- Trifluoromethylphenyl) diethoxysilane, di (4-trifluoromethylphenyl) dimethoxysilane, di (4-trifluoromethylphenyl) diethoxysilane, di (3,5-di (trifluoromethyl) phenyl) dimethoxysilane , Di (3,5-di (trifluoromethyl) phenyl) diethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, and particularly preferred compound is dimethyldimethoxysilane. Dimethyl diethoxy silane.
  • vinyltrialkoxysilane [3] include, but are not limited to, the following compounds: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, and vinyltriisopropoxysilane.
  • preferable compounds include vinyltrimethoxysilane and vinyltriethoxysilane.
  • trialkoxysilane [1], dialkoxysilane [2] and vinyltrialkoxysilane [3] is not particularly limited.
  • Trialkoxysilane [1], dialkoxysilane [2] and vinyltrialkoxysilane [3] may be used alone or in combination of two or more.
  • Trialkoxysilane [1] is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane and 3 , 5- (ditrifluoromethyl) phenyltriethoxysilane is selected from the group consisting of Dialkoxysilane [2] includes dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimeth
  • At least one trialkoxysilane [1] is selected from the group consisting of phenyltrimethoxysilane and phenyltriethoxysilane
  • One or more dialkoxysilane [2] is selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane
  • One or more vinyltrialkoxysilanes [3] are selected from the group consisting of vinyltrimethoxysilane and vinyltriethoxysilane.
  • the first alkoxysilane composition according to the present invention may further contain a tetraalkoxysilane represented by the following general formula [4]. Including tetraalkoxysilane [4] is preferable in that the mechanical strength of the cured product of the present invention is improved.
  • R 6 represents an alkyl group having 1 to 3 carbon atoms.
  • R 6 is preferably a methyl group or an ethyl group.
  • tetraalkoxysilane [4] include, but are not limited to, the following compounds: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.
  • preferred compounds include tetramethoxysilane and tetraethoxysilane.
  • trialkoxysilane [1], dialkoxysilane [2], vinyltrialkoxysilane [3] and tetraalkoxysilane [4] is not particularly limited.
  • the trialkoxysilane [1], dialkoxysilane [2], vinyltrialkoxysilane [3] and tetraalkoxysilane [4] may be used alone or in combination of two or more. .
  • Trialkoxysilane [1] is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane and 3 , 5- (ditrifluoromethyl) phenyltriethoxysilane is selected from the group consisting of Dialkoxysilane [2] includes dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimeth
  • At least one trialkoxysilane [1] is selected from the group consisting of phenyltrimethoxysilane and phenyltriethoxysilane
  • One or more dialkoxysilane [2] is selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane
  • At least one vinyltrialkoxysilane [3] is selected from the group consisting of vinyltrimethoxysilane and vinyltriethoxysilane
  • At least one tetraalkoxysilane [4] is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.
  • the mixing ratio of trialkoxysilane [1], dialkoxysilane [2] and vinyltrialkoxysilane [3] is not particularly limited.
  • the trialkoxysilane [1] and dialkoxysilane [2] are preferably blended at a molar ratio of 85:15 to 15:85, and particularly preferably 85:15 to 30:70. If it exists in this range, a hydrolysis polycondensation reaction will advance easily and the hydrolysis polycondensate of a desired average molecular weight can be obtained.
  • the amount of vinyltrialkoxysilane [3] is preferably 1 to 40 mol, preferably 3 to 20 mol, per 100 mol of the total amount of trialkoxysilane [1] and dialkoxysilane [2]. Is particularly preferred. If it exists in this range, the composition of this invention will show favorable hardening reactivity, and can obtain the hardened
  • the first alkoxysilane composition according to the present invention further contains tetraalkoxysilane [4], trialkoxysilane [1], dialkoxysilane [2], vinyltrialkoxysilane [3] and tetraalkoxysilane [4].
  • the amount of tetraalkoxysilane [4] is preferably 1 to 30 moles per 100 moles of the total amount of trialkoxysilane [1], dialkoxysilane [2] and vinyltrialkoxysilane [3]. Particularly preferred is 20 moles. If it exists in this range, the composition of this invention will show favorable hardening reactivity, and can obtain the hardened
  • the lower limit of the mass average molecular weight of the first silicone resin according to the present invention may be 3,800 or more, preferably 4,000 or more, particularly preferably 5,000 or more, and the upper limit is 20,000 or less. It is preferably 15,000 or less, and particularly preferably 10,000 or less.
  • the mass average molecular weight of the first silicone resin according to the present invention may be 3,800 to 20,000, and within this range, the composition of the present invention is suppressed from foaming, cracks and tack.
  • the composition of the present invention has an appropriate viscosity that is easy to handle. 4,000 to 15,000 are preferred, and among these, 5,000 to 10,000 are particularly preferred because a cured product having excellent mechanical strength can be obtained.
  • the mass average molecular weight is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting by a standard polystyrene calibration curve.
  • the viscosity of the first silicone resin according to the present invention is not particularly limited.
  • the viscosity at 25 ° C. is preferably 0.001 to 1,000,000 cP (centipoise), and more preferably 0.001 to 50,000 cP. If the viscosity exceeds 1,000,000 cP, the moldability may be inferior, but it is also possible to take a treatment to reduce the viscosity by heating.
  • the viscosity can be measured by a rotational viscometer or the like.
  • the content of CH 2 ⁇ CH—Si group in the first silicone resin according to the present invention is not particularly limited. 0.1 to 5.0 mmol / g is preferable, and 0.5 to 3.0 mmol / g is particularly preferable. Within this range, the curing reaction of the composition of the present invention is likely to proceed, and the cured product of the present invention exhibits good light transmittance at wavelengths of 365 nm, 405 nm, or both.
  • the content of CH 2 ⁇ CH—Si group is calculated by measuring the 1 H-NMR spectrum of the first silicone resin according to the present invention by adding an internal standard using a nuclear magnetic resonance apparatus. Can do.
  • the content of the HO—Si group in the first silicone resin according to the present invention is not particularly limited.
  • the HO—Si group content was determined by measuring the 29 Si-NMR spectrum and 1 H-NMR spectrum of the first silicone resin according to the present invention using a nuclear magnetic resonance apparatus, and combining these in a complementary manner. Can be used to calculate.
  • the manufacturing method of the 1st silicone resin which concerns on this invention is a method of carrying out the hydrolysis polycondensation of the 1st alkoxysilane composition which concerns on this invention.
  • a catalyst can also be used in order to allow the reaction to proceed efficiently.
  • the type of catalyst used may be an acidic catalyst or a basic catalyst.
  • the kind of acidic catalyst is not particularly limited, and examples thereof include acetic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, trifluoromethanesulfonic acid, tosylic acid, trifluoroacetic acid and the like.
  • the type of the basic catalyst is not particularly limited. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, pyridine, pKa (20 ° C. described later) And basic organic compounds having 9 or more in water).
  • a basic organic compound having a pKa (20 ° C. in water) of 9 or more is preferable because the molecular weight of the first alkoxysilane composition can be easily controlled.
  • the kind of the basic organic compound having a pKa of 9 or more is not particularly limited as long as it is an organic compound having a pKa of 9 or more.
  • Specific examples of the basic organic compound having a pKa of 9 or more used in the present invention include the following compounds: 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter referred to as “diazabicycloun”).
  • Decene ”or“ DBU ”) 1,5-diazabicyclo [4.3.0] -5-nonene (hereinafter sometimes referred to as“ diazabicyclononene ”or“ DBN ”) , Guanidine, tetramethylguanidine, 7-methyl-1,5,7-triazabicyclo [4.4.0] -5-decene, 1,5,7-triazabicyclo [4.4.0] -5 -Decene.
  • diazabicycloundecene and guanidine are preferable, and diazabicycloundecene is more preferable.
  • the amount of the catalyst used is not particularly limited.
  • the total molar amount of alkoxy groups in the system that is, 0.05 to 1.0 mol% is preferably used with respect to the total molar amount of alkoxy groups contained in the first alkoxysilane composition.
  • 0.1 to 0.5 mol% is preferable, and 0.2 to 0.4 mol% is particularly preferable.
  • the molecular weight of the resulting hydrolysis condensate can be easily controlled, and a hydrolysis condensate having a desired molecular weight can be obtained.
  • the total molar amount of alkoxy groups of the alkoxysilane contained in the first alkoxysilane composition that is, trialkoxy.
  • the total molar amount of alkoxy groups contained in silane [1], dialkoxysilane [2], vinyltrialkoxysilane [3], and tetraalkoxysilane (4). Is preferred. If it is in this range, hydrolysis of the alkoxysilane proceeds sufficiently, and the yield per unit volume of the reactor is good.
  • a reaction solvent may be used, and it is preferably used from the viewpoint of molecular weight control.
  • the type of the reaction solvent is not particularly limited as long as it does not inhibit the reaction for producing the first silicone resin.
  • examples include lipophilic organic solvents and hydrophilic organic solvents. These may be used singly or in combination of two or more. From the viewpoint of keeping the reaction system uniform, It is preferable to use a hydrophilic organic solvent in combination.
  • the solvent ratio in the case of using together is not specifically limited, As for the kind of solvent, it is preferable that a lipophilic organic solvent is an aromatic hydrocarbon and a hydrophilic organic solvent is alcohol.
  • lipophilic organic solvent examples include, but are not limited to, aromatic hydrocarbons such as toluene and xylene.
  • hydrophilic organic solvent examples include, but are not limited to, alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol.
  • the amount used in the case of using a reaction solvent is not particularly limited.
  • Total amount of alkoxysilane contained in the first alkoxysilane composition that is, alkoxy groups contained in trialkoxysilane [1], dialkoxysilane [2], vinyltrialkoxysilane [3], tetraalkoxysilane (4) Is preferably from 0.1 to 1000% by weight, particularly preferably from 1 to 300% by weight, based on the total amount.
  • reaction time is not particularly limited, but may be 1 hour or longer, or 48 hours or shorter.
  • reaction temperature is not specifically limited, 20 degreeC or more may be sufficient, 30 degreeC or more is preferable, 120 degreeC or less may be sufficient, and 70 degreeC or less is preferable. Of these, 20 to 120 ° C. is preferable, and 30 to 70 ° C. is particularly preferable.
  • trialkoxysilane [1], dialkoxysilane [2] and vinyltrialkoxysilane [3], and optionally tetraalkoxysilane [4] are allowed to reach room temperature (especially an ambient temperature not heated or cooled, usually 15 to 30 ° C. The same applies hereinafter.)
  • a catalyst is further added, and water and a reaction solvent are added to obtain a blended solution.
  • the order of input at this time is not limited to this, and can be input in an arbitrary order.
  • a hydrolysis polycondensate can be obtained by advancing the reaction at a predetermined temperature for a predetermined time while stirring the blended solution.
  • the reaction vessel may be equipped with a reflux device. It is preferable to do.
  • the separation method includes an extraction method. Specifically, after the temperature of the reaction solution after the reaction described above is lowered to room temperature, the first silicone resin according to the present invention present in the reaction system is extracted by contacting with an extraction solvent. When a catalyst is contained in the solution after extraction, the removal is performed.
  • the removal method is not particularly limited. For example, when a basic organic compound having a pKa of 9 or more is used as the catalyst, the catalyst can be removed by washing the solution after extraction with an acid such as dilute hydrochloric acid. Next, the first silicone resin according to the present invention can be separated with high purity by passing through the extraction solvent under reduced pressure.
  • a non-aqueous organic solvent can be used as the extraction solvent, and specific examples include aromatic hydrocarbons and ethers. More specifically, examples include toluene, diethyl ether, isopropyl ether, dibutyl ether, and the like, but are not limited thereto.
  • the component (B) is a silicone resin having a H—Si group (second silicone resin).
  • the component (B) is not particularly limited as long as it is a silicone resin having an H—Si group.
  • the following “(B-1) component”, “(B-2) component” or “(B-3) component” may be used, and the component (B-1) is easy to mix with the component (A). Is preferred. These may be used alone or in combination of two or more.
  • (B-1) component The component (B-1) hydrolytically polycondenses a second alkoxysilane composition containing at least a trialkoxysilane represented by the following general formula [5] and a dialkoxysilane represented by the general formula [6].
  • a hydrolyzed polycondensate having a Si—OH group and a silane compound represented by the following general formula [8-1], [8-2], [8-3] or [8-4] A silicone resin having a Si—H group obtained by reacting at least one of the above.
  • hydrolyzed polycondensate having a Si—OH group obtained by hydrolytic condensation of the second alkoxysilane composition is referred to as “hydrolyzed polycondensate [B-1-I]”. May be expressed.
  • R 7 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • R 8 represents an alkyl group having 1 to 3 carbon atoms, and the three R 8 may be the same or different from each other.
  • R 7 is preferably a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group, and particularly preferably a phenyl group.
  • R 8 is preferably a methyl group or an ethyl group.
  • R 9 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and two R 9 may be the same or different from each other.
  • R 10 represents an alkyl group having 1 to 3 carbon atoms, and two R 10 may be the same or different from each other.
  • R 9 is preferably a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group, and particularly preferably a methyl group.
  • R 10 is preferably a methyl group or an ethyl group.
  • R 12 represents an alkyl group having 1 to 3 carbon atoms, and two R 12 in each formula may be the same or different from each other.
  • R 13 represents an alkyl group having 1 to 3 carbon atoms.
  • trialkoxysilane [5] include, but are not limited to, the following compounds: methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, ethyltripropoxysilane, ethyltriisopropoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltriisopropoxysilane, isopropyltrimethoxysilane , Isopropyltriethoxysilane, isopropyltripropoxysilane, isopropyltriisopropoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane,
  • preferred compounds include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, 3 -(Trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane, 3, 5- (ditrifluoromethyl) phenyltriethoxysilane can be mentioned, and particularly preferred compounds include phenyltrimethoxysilane and phenyltriethoxysilane.
  • dialkoxysilane [6] include, but are not limited to, the following compounds: dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyl Diethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, di (n-propyl) dimethoxysilane, di (n-propyl) diethoxysilane, di (n-propyl) dipropoxysilane, di (n-propyl) Diisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, di (n-butyl) dimethoxysilane, di (n-butyl
  • preferred compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, di (3-trifluoromethylphenyl) dimethoxysilane, di (3- Trifluoromethylphenyl) diethoxysilane, di (4-trifluoromethylphenyl) dimethoxysilane, di (4-trifluoromethylphenyl) diethoxysilane, di (3,5-di (trifluoromethyl) phenyl) dimethoxysilane , Di (3,5-di (trifluoromethyl) phenyl) diethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, and particularly preferred compound is dimethyldimethoxysilane. Dimethyl diethoxy silane.
  • trialkoxysilane [5] and dialkoxysilane [6] are not particularly limited. Trialkoxysilane [5] and dialkoxysilane [6] may be used alone or in combination of two or more.
  • Trialkoxysilane [5] is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane and 3 , 5- (ditrifluoromethyl) phenyltriethoxysilane is selected from the group consisting of Dialkoxysilane [6] includes dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimeth
  • At least one trialkoxysilane [5] is selected from the group consisting of phenyltrimethoxysilane and phenyltriethoxysilane
  • One or more dialkoxysilanes [6] are selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane.
  • the second alkoxysilane composition according to the present invention may further contain a tetraalkoxysilane represented by the following general formula [7]. Including tetraalkoxysilane [7] is preferable because the mechanical strength of the cured product of the present invention is improved.
  • R 11 represents an alkyl group having 1 to 3 carbon atoms.
  • R 11 is preferably a methyl group or an ethyl group.
  • tetraalkoxysilane [7] include, but are not limited to, the following compounds: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetraisopropoxysilane.
  • preferred compounds include tetramethoxysilane and tetraethoxysilane.
  • the combination of trialkoxysilane [5], dialkoxysilane [6] and tetraalkoxysilane [7] is not particularly limited.
  • the trialkoxysilane [5], dialkoxysilane [6], and tetraalkoxysilane [7] may be used alone or in combination.
  • Trialkoxysilane [5] is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane and 3 , 5- (ditrifluoromethyl) phenyltriethoxysilane is selected from the group consisting of Dialkoxysilane [6] includes dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimeth
  • At least one trialkoxysilane [5] is selected from the group consisting of phenyltrimethoxysilane and phenyltriethoxysilane
  • One or more dialkoxysilane [6] is selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane
  • One or more tetraalkoxysilanes [7] are selected from the group consisting of tetramethoxysilane and tetraethoxysilane.
  • the mixing ratio of trialkoxysilane [5] and dialkoxysilane [6] is not particularly limited.
  • the trialkoxysilane [5] and dialkoxysilane [6] are preferably blended at a molar ratio of 85:15 to 15:85, particularly preferably 85:15 to 30:70. Within this range, the hydrolysis polycondensation reaction tends to proceed, and a hydrolysis polycondensation product [B-1-I] having a desired average molecular weight can be obtained.
  • the compounding ratio of trialkoxysilane [5], dialkoxysilane [6] and tetraalkoxysilane [7] is particularly limited. Not.
  • the amount of tetraalkoxysilane [7] is preferably 1 to 60 mol, particularly preferably 1 to 30 mol, per 100 mol of the total amount of trialkoxysilane [5] and dialkoxysilane [6]. . If it exists in this range, the composition of this invention will show favorable hardening reactivity, and can obtain the hardened
  • silane compound [8-1] include, but are not limited to, the following compounds: dimethylchlorosilane, diethylchlorosilane, di (n-propyl) chlorosilane, diisopropylchlorosilane.
  • preferred compounds include dimethylchlorosilane and diethylchlorosilane.
  • silane compound [8-2] include, but are not limited to, the following compounds: dimethylsilanol, diethylsilanol, di (n-propyl) silanol, diisopropylsilanol.
  • preferred compounds include dimethylsilanol and diethylsilanol.
  • silane compound [8-3] include, but are not limited to, the following compounds: dimethylmethoxysilane, dimethylethoxysilane, dimethylpropoxysilane, dimethylisopropoxysilane, diethylmethoxysilane, diethylethoxysilane , Diethylpropoxysilane, diethylisopropoxysilane, di (n-propyl) methoxysilane, di (n-propyl) ethoxysilane, di (n-propyl) propoxysilane, di (n-propyl) isopropoxysilane, diisopropylmethoxysilane , Diisopropylethoxysilane, diisopropylpropoxysilane, diisopropylisopropoxysilane.
  • preferred compounds include dimethylmethoxysilane and dimethylmethoxysilane.
  • silane compound [8-4] include, but are not limited to, the following compounds: tetramethyldisiloxane, tetraethyldisiloxane, tetra (n-propyl) disiloxane, and tetraisopropyldisiloxane.
  • preferred compounds include dimethyldisiloxane and diethyldisiloxane.
  • the hydrolysis polycondensation product [B-1-I] can be obtained by hydrolytic condensation of the second alkoxysilane composition.
  • the method for producing the hydrolyzed polycondensate [B-1-I] is to hydrolyze and condense the second alkoxysilane composition, and other conditions are not particularly limited.
  • the hydrolyzed polycondensate [B-1-I] water may be used.
  • the total molar amount of alkoxy groups of the alkoxysilane contained in the second alkoxysilane composition that is, It is preferable to use 0.5 to 5 times the total molar amount of alkoxy groups contained in trialkoxysilane [5], dialkoxysilane [6] and tetraalkoxysilane (7). If it is in this range, hydrolysis of the alkoxysilane proceeds sufficiently, and the yield per unit volume of the reactor is good.
  • a reaction solvent may be used, and it is preferably used from the viewpoint of molecular weight control.
  • the type of the reaction solvent is not particularly limited as long as the reaction for producing the hydrolysis polycondensate [B-1-I] is not inhibited.
  • Examples include lipophilic organic solvents and hydrophilic organic solvents. These may be used singly or in combination of two or more. From the viewpoint of keeping the reaction system uniform, It is preferable to use a hydrophilic organic solvent in combination.
  • the solvent ratio in the case of using together is not specifically limited, As for the kind of solvent, it is preferable that a lipophilic organic solvent is aromatic hydrocarbons and a hydrophilic organic solvent is alcohol.
  • lipophilic organic solvent examples include, but are not limited to, aromatic hydrocarbons such as toluene and xylene.
  • hydrophilic organic solvent examples include, but are not limited to, alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol.
  • the amount used in the case of using a reaction solvent is not particularly limited. 10 to the total amount of alkoxysilanes contained in the second alkoxysilane composition, that is, the total amount of alkoxy groups contained in trialkoxysilane [5], dialkoxysilane [6] and tetraalkoxysilane (7). It is preferably ⁇ 1000 mass%, particularly preferably 30 to 300 mass%.
  • reaction time is not particularly limited, but may be 2 hours or more, or 48 hours or less.
  • reaction temperature is not specifically limited, 60 degreeC or more may be sufficient, 80 degreeC or more is preferable, 120 degreeC or less may be sufficient, and 100 degreeC or less is preferable.
  • 60 to 120 ° C. is preferable, and 80 to 100 ° C. is particularly preferable.
  • a catalyst can also be used in order to allow the reaction to proceed efficiently.
  • the type of catalyst used may be an acidic catalyst or a basic catalyst.
  • the use of an acidic catalyst is preferred because the molecular weight of the hydrolyzed polycondensate [B-1-I] can be easily controlled.
  • the kind of acidic catalyst is not particularly limited. For example, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, trifluoromethanesulfonic acid, tosylic acid, trifluoroacetic acid and the like can be mentioned.
  • acetic acid hydrochloric acid, nitric acid, sulfuric acid, and hydrofluoric acid are preferable, and acetic acid is more preferable because the removal of the acid catalyst after the reaction is easy.
  • the kind of basic catalyst is not specifically limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, pyridine and the like.
  • the amount used when using a catalyst is not particularly limited.
  • the amount is preferably 0.001 to 5% by mass, particularly preferably 0.005 to 1% by mass, based on the total amount of the second alkoxysilane composition, the reaction solvent and water.
  • trialkoxysilane [5] and dialkoxysilane [6], and optionally tetraalkoxysilane [7] are added to the reaction vessel at room temperature, water is further added, a catalyst is optionally added, and a reaction solvent is optionally added. In addition, a mixed solution is obtained.
  • the order of input at this time is not limited to this, and can be input in an arbitrary order.
  • the hydrolysis polycondensate [B-1-I] can be obtained by advancing the reaction at a predetermined temperature for a predetermined time while stirring the blended solution.
  • the reaction vessel may be equipped with a reflux device. It is preferable to do.
  • the hydrolyzed polycondensate [B-1-I] may be separated and purified from the reaction system.
  • This separation method is not particularly limited.
  • the separation method include an extraction method. Specifically, the reaction solution after the above reaction is cooled to room temperature, and then contacted with an extraction solvent to extract the hydrolyzed polycondensate [B-1-I] present in the reaction system.
  • a catalyst is contained in the solution after extraction, the removal is performed.
  • the removal method is not particularly limited. For example, if the used catalyst (for example, acetic acid) is water-soluble, the catalyst can be removed by washing the solution after extraction with water.
  • the water dissolved in the system may be removed by a drying treatment such as adding a desiccant if desired.
  • a drying treatment such as adding a desiccant if desired.
  • the hydrolysis polycondensate [B-1-I] can be separated with high purity by removing the extraction solvent under reduced pressure.
  • a non-aqueous organic solvent can be used as the extraction solvent, and specific examples include aromatic hydrocarbons and ethers. More specifically, examples include toluene, diethyl ether, isopropyl ether, dibutyl ether, and the like, but are not limited thereto.
  • the separated and purified hydrolyzed polycondensate [B-1-I] may be further subjected to a condensation reaction by heating in a solvent under reflux or heating and stirring without solvent. As a result, the molecular weight of the hydrolyzed polycondensate [B-1-I] can be increased.
  • the hydrolysis polycondensate [B-1-I] and the solvent are put into a reaction vessel capable of heating and refluxing to obtain a solution.
  • the solution is heated to reflux and azeotroped with water generated in the system as the condensation proceeds.
  • tosylic acid, p-toluenesulfonic acid or the like may be added to the solution and heated to reflux.
  • the type of the solvent to be used is not particularly limited as long as it can dissolve the hydrolysis polycondensate [B-1-I] and can be heated to reflux.
  • Specific examples include aromatic hydrocarbons such as toluene, xylene, and benzene, ethers such as diethyl ether and diisopropyl ether, and esters such as ethyl acetate.
  • the hydrolysis polycondensate [B-1-I] is charged into a reaction vessel capable of being heated and stirred, heated at 100 to 150 ° C., and stirred for 6 to 18 hours.
  • the reaction vessel is preferably provided with a reflux device. After heating and stirring, the content liquid is cooled to room temperature.
  • the method for producing the component (B-1) is not particularly limited except for the reaction of the hydrolysis polycondensate [B-1-I] with the silane compound [8].
  • the first method is to react a hydrolysis polycondensate [B-1-I] with a chlorosilane compound [8-1], which is a kind of silane compound [8], in a water-insoluble organic solvent.
  • (B-1) refers to a method for producing the component.
  • the second method is a hydrolysis polycondensate [B-1-I] and a silanol compound [8-2], a monoalkoxysilane compound [8-3] or disiloxane which is a kind of silane compound [8].
  • This refers to a method for producing the component (B-1) by reacting the compound [8-4] in the presence of an acid in a mixed solvent of a water-insoluble organic solvent and an alcoholic solvent.
  • “First method” In the first method, first, a hydrolysis polycondensate [B-1-I] and a nonaqueous organic solvent are put in a predetermined amount in a reaction vessel, and the hydrolysis polycondensation product [B-1-I] is added. Dissolve. Next, a predetermined amount of the chlorosilane compound [8-1] is added to the solution while stirring at about 0 to about 10 ° C. The addition method is not particularly limited, but dropping is preferable. After completion of the addition, the reaction is allowed to proceed by stirring for 0.5 to 18 hours while maintaining 0 ° C. to room temperature. Thereafter, by terminating the reaction, the component (B-1) can be obtained.
  • the amount of hydrolysis polycondensation product [B-1-I] and chlorosilane compound [8-1] used is not particularly limited. From the viewpoint of the physical properties of the component (B-1), it is preferable to use 0.2 to 10 mmol of the chlorosilane compound [8-1] with respect to 1 g of the hydrolyzed polycondensate [B-1-I].
  • the type of the water-insoluble organic solvent to be used is not particularly limited as long as it is water-insoluble and does not inhibit the reaction for producing the component (B-1).
  • aromatic hydrocarbons and ethers are preferable. Specific examples include toluene, diethyl ether, tetrahydrofuran, diisopropyl ether, and the like, but are not limited thereto.
  • the amount of the water-insoluble organic solvent used is preferably 50 to 1000% by mass, particularly preferably 300 to 700% by mass, with respect to 1 g of the hydrolyzed polycondensate [B-1-I].
  • the method for terminating the reaction is not particularly limited.
  • the reaction is terminated by dropping water (preferably ion-exchanged water) into the reaction system.
  • water preferably ion-exchanged water
  • This separation and purification method is not particularly limited.
  • a method of extracting can be mentioned. Specifically, the organic layer is separated from the reaction solution after the above reaction, and then the organic layer is washed with an acid and further washed with water. Next, a desiccant is added to the washed organic layer to remove water dissolved in the system.
  • the component (B-1) can be separated with high purity by removing the desiccant and removing the non-aqueous organic solvent under reduced pressure. At this time, water may be simultaneously removed under reduced pressure in the process of removing the non-aqueous organic solvent under reduced pressure without using a desiccant.
  • the component (B-1) after separation is preferably further freed of water contained in the component (B-1) by heating and stirring under reduced pressure without a solvent. The heating temperature at this time is not particularly limited, but is usually 100 to 130 ° C.
  • a hydrolysis polycondensation product [B-1-I], a non-aqueous organic solvent, and optionally an alcoholic solvent are put in a predetermined amount in a reaction vessel, and the hydrolysis polycondensation product is added.
  • [B-1-I] is dissolved.
  • a predetermined amount of silanol compound [8-2], monoalkoxysilane compound [9-3] or disiloxane compound [9-4] is added to the solution.
  • a catalyst for proceeding the hydrolysis and dehydration condensation reaction is added to the reaction system, and the reaction system is stirred for 1 to 48 hours at room temperature to proceed the reaction. Then, (A) component can be obtained by terminating reaction.
  • the amount of the hydrolyzed polycondensate (I) and the silanol compound [8-2], monoalkoxysilane compound [8-3] or disiloxane compound [8-4] used is not particularly limited. .
  • silanol compound [8-2], monoalkoxysilane compound [8-3] or disiloxane is used per 1 g of hydrolyzed polycondensate [B-1-I].
  • the compound [8-4] is preferably used in a range where the total content of Si—H groups is 0.2 to 10 mmol.
  • the type of the water-insoluble organic solvent to be used is not particularly limited as long as the reaction for producing the component (B-1) is not inhibited.
  • aromatic hydrocarbons and ethers are preferable. Specific examples include toluene, diethyl ether, tetrahydrofuran, diisopropyl ether, and the like, but are not limited thereto.
  • the amount of the water-insoluble organic solvent to be used is preferably 50 to 1000% by mass, particularly preferably 100 to 500% by mass, with respect to 1 g of the hydrolyzed polycondensate [B-1-I].
  • the type of alcohol solvent to be used is not particularly limited as long as the reaction for producing the component (B-1) is not inhibited.
  • alcohols having 1 to 4 carbon atoms are preferred. Specific examples include methanol, ethanol, 1-propanol, 2-propanol, butanol and the like, but are not limited thereto.
  • the amount of the alcohol solvent used is preferably 10 to 500% by mass, particularly preferably 50 to 300% by mass, based on 1 g of the hydrolyzed polycondensate (I).
  • the second method it is preferable to use a mixed solvent of a water-insoluble organic solvent and an alcohol solvent according to the type of catalyst used.
  • a proton acid catalyst is used, the reactivity can be improved by using this mixed solvent.
  • the type of catalyst to be used is not particularly limited as long as it has an effect of promoting the reaction for producing the component (B-1).
  • inorganic acids are preferred. Specific examples include nitric acid, hydrochloric acid, sulfuric acid and the like, but are not limited thereto.
  • the amount of the catalyst used is preferably from 0.0001 to 10 mmol%, particularly preferably from 0.005 to 5 mmol%, based on 1 g of the hydrolyzed polycondensate [B-1-I].
  • the method for terminating the reaction is not particularly limited.
  • the reaction is terminated by adding water (preferably ion-exchanged water) to the reaction system and stirring.
  • water preferably ion-exchanged water
  • purify the component (B-1) by separating it from the reaction system from the viewpoint of handling the component (B-1).
  • This separation and purification method is not particularly limited.
  • a method of extracting can be mentioned. Specifically, the organic layer is separated from the solution after the above reaction. Next, the organic layer is washed with water (preferably ion-exchanged water), and further a desiccant is added to remove water dissolved in the system.
  • the desiccant is removed from the organic layer, and the water-insoluble organic solvent is removed under reduced pressure, whereby the component (B-1) can be separated with high purity.
  • water may be simultaneously removed under reduced pressure in the process of removing the non-aqueous organic solvent under reduced pressure without using a desiccant.
  • the component (B-1) after separation is preferably further freed of water contained in the component (B-1) by heating and stirring under reduced pressure without a solvent.
  • the heating temperature at this time is not particularly limited, but is usually 100 to 130 ° C.
  • (B-2) component The component (B-2) is a cyclic siloxane having a Si—H group.
  • the component (B-2) is not particularly limited as long as it is a cyclic siloxane having a Si—H group, and specific examples include the following compounds: 2,4,6-trimethylcyclotrisiloxane, 2,4, 6,8, -tetramethylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10,12-hexamethylcyclohexasiloxane, 2,4,6 , 8,10,12,14-heptamethylcycloheptasiloxane.
  • 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8, -tetramethylcyclotetrasiloxane and 2,4,6,8,10-pentamethylcyclopentasiloxane are preferable.
  • (B-3) component The component (B-3) is obtained by hydrolyzing and condensing a third alkoxysilane composition containing at least a dialkoxysilane represented by the following general formula [9] and a dialkoxyhydrosilane represented by the general formula [10].
  • This is a silicone resin having a Si—H group.
  • R 14 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and two R 14 may be the same or different from each other.
  • R 15 represents an alkyl group having 1 to 3 carbon atoms, and the two R 15 may be the same or different from each other.
  • R 14 is preferably a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group, and the methyl group and the phenyl group are Particularly preferred.
  • R 15 is preferably a methyl group or an ethyl group.
  • R 16 represents an aliphatic hydrocarbon group having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • R 17 represents an alkyl group having 1 to 3 carbon atoms, and the two R 17 may be the same or different from each other.
  • R 16 is preferably a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group, and the methyl group and the phenyl group are Particularly preferred.
  • R 17 is preferably a methyl group or an ethyl group.
  • dialkoxysilane [9] include, but are not limited to, the following compounds: dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, diethyldimethoxysilane, diethyl Diethoxysilane, diethyldipropoxysilane, diethyldiisopropoxysilane, di (n-propyl) dimethoxysilane, di (n-propyl) diethoxysilane, di (n-propyl) dipropoxysilane, di (n-propyl) Diisopropoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldipropoxysilane, diisopropyldiisopropoxysilane, di (n-butyl) dimethoxysilane, di (n-butyl
  • preferred compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, di (3-trifluoromethylphenyl) dimethoxysilane, di (3- Trifluoromethylphenyl) diethoxysilane, di (4-trifluoromethylphenyl) dimethoxysilane, di (4-trifluoromethylphenyl) diethoxysilane, di (3,5-di (trifluoromethyl) phenyl) dimethoxysilane , Di (3,5-di (trifluoromethyl) phenyl) diethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, and particularly preferred compound is dimethyldimethoxysilane. Dimethyl diethoxy silane, diphenyldime
  • dialkoxyhydrosilane [10] examples include, but are not limited to, the following compounds: methyldimethoxyhydrosilane, methyldiethoxyhydrosilane, methyldipropoxyhydrosilane, methyldiisopropoxyhydrosilane, ethyldimethoxyhydrosilane, ethyl Diethoxyhydrosilane, ethyldipropoxyhydrosilane, ethyldiisopropoxyhydrosilane, n-propyldimethoxyhydrosilane, n-propyldiethoxyhydrosilane, n-propyldipropoxyhydrosilane, n-propyldiisopropoxyhydrosilane, isopropyldimethoxyhydrosilane, isopropyldiethoxy Hydrosilane, isopropyldipropoxyhydrosilane, isopropyldiisopropoxyhydr
  • preferred compounds include methyldimethoxyhydrosilane, methyldiethoxyhydrosilane, ethyldimethoxyhydrosilane, ethyldiethoxyhydrosilane, phenyldimethoxyhydrosilane, phenyldiethoxyhydrosilane, 3-trifluoromethylphenyldimethoxyhydrosilane, 3-trifluoromethylphenyldisilane.
  • Particularly preferred compounds include methyldimethoxyhydrosilane, methyldiethoxyhydrosilane, Dimethoxy hydrosilane, phenyl diethoxy hydrosilane.
  • dialkoxysilane [9] and dialkoxyhydrosilane [10] are not particularly limited. Dialkoxysilane [9] and dialkoxyhydrosilane [10] may be used alone or in combination of two or more.
  • Dialkoxysilane [9] is dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, di (3-trifluoromethylphenyl) dimethoxysilane, di (3 -Trifluoromethylphenyl) diethoxysilane, di (4-trifluoromethylphenyl) dimethoxysilane, di (4-trifluoromethylphenyl) diethoxysilane, di (3,5-di (trifluoromethyl) phenyl) dimethoxy One or more selected from the group consisting of silane, di (3,5-di (trifluoromethyl) phenyl) diethoxysilane, phenylmethyldimethoxysilane and phenylmethyldiethoxysilane, Dialkoxyhydrosilane
  • One or more are selected from the group consisting of hydrosilanes.
  • Dialkoxysilane [9] is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane and phenylmethyldiethoxysilane
  • the dialkoxyhydrosilane [10] is selected from the group consisting of methyldimethoxyhydrosilane, methyldiethoxyhydrosilane, phenyldimethoxyhydrosilane, and phenyldiethoxyhydrosilane.
  • the blending ratio of dialkoxysilane [9] and dialkoxyhydrosilane [10] is not particularly limited.
  • the dialkoxysilane [9] and the dialkoxyhydrosilane [10] are preferably blended at a molar ratio of 95: 5 to 5:95, particularly preferably 80:20 to 20:80. If it exists in this range, the composition of this invention will show favorable hardening reactivity, and can obtain the hardened
  • the method for producing the component is hydrolytic condensation of the third alkoxysilane composition, and other conditions are not particularly limited.
  • the component (B-3) can be produced according to the method for producing the hydrolysis polycondensate [B-1-I] described above. That is, in the above-described method for producing the hydrolysis polycondensate [B-1-I] according to the present invention, “trialkoxysilane [5], dialkoxysilane [6] and tetraalkoxysilane [7]” are converted to “dialkoxysilane”.
  • the alkoxysilane [9] and dialkoxyhydrosilane [10] are replaced, the “second alkoxysilane composition” is replaced with the “third alkoxysilane composition”, and the “hydrolysis polycondensate [B-1-I” is replaced. ] ”Can be replaced with“ component (B-3) ”to describe an example of a method for producing the component (B-3).
  • the component (B) may be the following commercially available silicone resin: Methylhydrosiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated (manufactured by Gelest): HMS-013, HMS-031, HMS-064, HMS-071, HMS-082, HMS-151, HMS-301, HMS-501 , Methylhydrosiloxane-dimethylsiloxane copolymer, hydride terminal (manufactured by Gelest): HMS-H271, Polymethylhydrosiloxane, trimethylsiloxy end (manufactured by Gelest): HMS-991, HMS-992, HMS-993, Polyethylhydrosiloxane, triethylsiloxy end (manufactured by Gelest): HES-992, Polyphenyl- (di)
  • the mass average molecular weight of the component (B) is not particularly limited, but is preferably 600 to 20,000, particularly preferably 900 to 10,000. Within this range, the cured product of the present invention has good mechanical strength.
  • the viscosity of a component is not specifically limited. From the viewpoint of handling workability, the viscosity at 25 ° C. is preferably 0.001 to 1,000,000 cP (centipoise), more preferably 0.001 to 50,000 cP. If the viscosity exceeds 1,000,000 cP, the moldability may be inferior, but it is also possible to take a treatment to reduce the viscosity by heating.
  • the component (B) always has an H—Si group, and its content is not particularly limited. 0.1 to 5.0 mmol / g is preferable, and 0.5 to 3.0 mmol / g is particularly preferable. Within this range, the composition of the present invention has good moldability.
  • the content of the H—Si group can be calculated by measuring the 1 H-NMR spectrum of the component (B) using a nuclear magnetic resonance apparatus and using an internal standard apparatus.
  • the content of the HO—Si group in the component (B) is not particularly limited. 0.5 to 5.0 mmol / g is preferable, and 1.0 to 3.5 mmol / g is particularly preferable. Within this range, bubbles are unlikely to occur in the cured product of the present invention.
  • the content of the HO—Si group is calculated by measuring the 29 Si-NMR spectrum and the 1 H-NMR spectrum of the component (B) using a nuclear magnetic resonance apparatus, and using these in a complementary combination. be able to.
  • Component (C) is a hydrosilylation catalyst, and promotes an addition curing reaction (hydrosilylation reaction) between the CH 2 ⁇ CH—Si group in component (A) and the H—Si group in component (B). Is blended into.
  • various catalysts that promote the hydrosilylation reaction can be used.
  • the component (C) one type may be used alone, or two or more types may be used in combination.
  • Examples of the component (C) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Among these, a platinum-based catalyst is preferable because the transparency of the sealing material can be increased.
  • platinum catalyst examples include platinum powder, chloroplatinic acid, complexes of chloroplatinic acid and alcohols, aldehydes, ketones, platinum-olefin complexes, platinum-alkenylsiloxane complexes, platinum-carbonyl complexes, and the like.
  • platinum-carbonylvinylmethyl complex platinum-divinyltetramethyldisiloxane complex (cursed catalyst), platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde complex, platinum-phosphine complex, dicarbonyldichloroplatinum and the like.
  • platinum-divinyltetramethyldisiloxane complex cursed catalyst
  • platinum-cyclovinylmethylsiloxane complex platinum-cyclovinylmethylsiloxane complex, and the like are preferable.
  • the compounding ratio of the component (A) and the component (B) in the composition of the present invention is not particularly limited. It is preferable to blend based on the molar ratio of CH 2 ⁇ CH—Si group in component (A) to H—Si group in component (B). Specifically, the ratio of the number of moles of CH 2 ⁇ CH—Si groups in component (A) to the number of moles of H—Si groups in component (B) is within the range of 1: 4 to 1: 1. Preferably there is. Within this range, the composition of the present invention exhibits good moldability and good heat-resistant transparency.
  • the amount of component (C) in the composition of the present invention is not particularly limited. Based on the total mass of component (A), component (B), and component (C), platinum, rhodium, or palladium metal atoms in component (C) are 0.003 to 10. 0 ppm is preferable, and 0.003 to 5.0 ppm is particularly preferable. Within this range, the composition of the present invention exhibits good curing reactivity, and the cured product of the present invention exhibits good heat-resistant transparency. Even within this range, the smaller the amount of component (C), the better the heat-resistant transparency, so the smaller the amount of component (C), the better.
  • the composition of the present invention is intended to improve the storage stability and handling workability of the composition and to adjust the hydrosilylation reactivity in the curing process.
  • a curing retarder may be blended. Since the composition of the present invention can be made into a cured product at a relatively low temperature, it can be suitably used for application / sealing to a heat-sensitive optical semiconductor member. On the other hand, depending on the coating / sealing work environment, it may be preferable to blend a curing retarder in order to adjust the curing rate from the viewpoint of storage stability over time and handling workability of the composition.
  • the kind of the curing retarder is not particularly limited as long as it is a compound having a curing retardation effect with respect to the component (C), and conventionally known ones can also be used.
  • a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, a nitrogen-containing compound, an organic sulfur compound, an organic peroxide, and the like can be given. These compounds may be used alone or in combination.
  • the compound containing an aliphatic unsaturated bond examples include 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyne- Examples include propargyl alcohols such as 3-ol and 1-ethynyl-1-cyclohexanol, ene-yne compounds, maleic esters such as maleic anhydride and dimethyl maleate, and the like.
  • organic phosphorus compound examples include triorganophosphines, diorganophosphines, organophosphines, and triorganophosphites.
  • nitrogen-containing compounds include N, N, N ′, N′-tetrasubstituted ethylene compounds such as N, N, N ′, N′-tetramethylethylenediamine and N, N, N ′, N′-tetraethylethylenediamine.
  • Alkylene diamines N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethyl-1,3-propanediamine N, N-dibutyl-1,4-butanediamine, and the like, trisubstituted amines such as tributylamine, benzotriazole, and 2,2′-bipyridine.
  • organic sulfur compound examples include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide, and the like.
  • organic peroxide examples include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate.
  • curing retardants compounds containing aliphatic unsaturated bonds and nitrogen-containing compounds are preferred, and maleic esters, propargyl alcohols, N, N, N ′, N′-tetrasubstituted alkylenediamines are preferred.
  • maleic esters, propargyl alcohols, N, N, N ′, N′-tetrasubstituted alkylenediamines are preferred.
  • Preferred are dimethyl maleate, 2-methyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, and N, N, N ′, N′-tetramethylethylenediamine.
  • the blending amount of these curing retarders is not particularly limited. You may mix
  • the degree of the retarding effect of the retarder varies depending on the chemical structure of the retarder. Therefore, it is preferable to adjust the blending amount to an optimal amount depending on the type of the curing retarder used. By adding an optimum amount of the retarder, the composition has excellent long-term storage stability at room temperature and heat curability.
  • an adhesion-imparting agent may be further blended for the purpose of improving the adhesion.
  • the adhesion-imparting agent include silane coupling agents and hydrolysis condensates thereof.
  • silane coupling agents include epoxy group-containing silane coupling agents such as ⁇ -glycidoxypropyltrimethoxysilane, (meth) acryl group-containing silane coupling agents, isocyanate group-containing silane coupling agents, and isocyanurate group-containing silanes.
  • Examples include known coupling agents, amino group-containing silane coupling agents, mercapto group-containing silane coupling agents, and the like.
  • the amount of the adhesion-imparting agent is not particularly limited. It may be 1 to 20% by mass, preferably 5 to 15% by mass, based on the total mass of the composition of the present invention.
  • An antioxidant may be further added to the composition of the present invention in order to suppress the occurrence of coloring and oxidative degradation of the cured product.
  • antioxidants include phenolic antioxidants, phosphorus antioxidants, and amine antioxidants. More specifically, 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 4,4′-butylidenebis ( 3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), etc. . These may be used individually by 1 type and may use 2 or more types together.
  • the blending amount of the antioxidant is not particularly limited as long as it is within the range that does not impair the characteristics such as transparency of the cured product of the present invention and is an effective amount as an antioxidant.
  • the total mass of the composition of the present invention may be 0.1 to 1,000 ppm, and preferably 10 to 500 ppm. Within this range, the ability to prevent oxidation is sufficiently exhibited, and a cured product having excellent engineering characteristics can be obtained without occurrence of coloring, white turbidity, oxidative degradation, and the like.
  • a light stabilizer may be further added to the composition of the present invention.
  • a hindered amine stabilizer that captures radicals generated by photooxidation degradation is preferably used, and the antioxidant effect can be further improved by using it together with the above-mentioned antioxidant.
  • Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, ADK STAB LA-77Y ( And ADEKA STAB LA-52 (manufactured by ADEKA Corporation).
  • the blending amount of the light stabilizer is not particularly limited as long as it is in an amount that does not impair the characteristics such as transparency of the cured product of the present invention and is an effective amount as a light stabilizer. It may be 0.01 to 5.0% by mass, preferably 0.05 to 0.5% by mass, based on the total mass of the composition of the present invention.
  • Fluorescent material may be further blended into the composition of the present invention.
  • the type of the phosphor is not particularly limited. For example, yellow, which is widely used for light emitting diodes (LEDs), such as oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, oxysulfide phosphors, Examples include red, green, and blue light emitting phosphors.
  • oxide phosphors include yttrium, aluminum, and garnet-based YAG green to yellow light-emitting phosphors that include cerium ions, terbium, aluminum, and garnet-based TAG-based yellow light-emitting phosphors that include cerium ions, cerium, Examples include silicate green to yellow light emitting phosphors containing europium ions.
  • Examples of the oxynitride phosphor include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions.
  • nitride-based phosphors examples include calcium, strontium, aluminum, silicon, nitrogen-based casoon-based red light-emitting phosphors including europium ions.
  • Examples of sulfide-based phosphors include ZnS-based green color phosphors including copper ions and aluminum ions.
  • Examples of the oxysulfide phosphor include Y 2 O 2 S red light-emitting phosphor containing europium ions.
  • These phosphors may be used alone or in combination of two or more.
  • the amount of the phosphor is not particularly limited. It may be 10 to 70% by mass, preferably 20 to 50% by mass, based on the total mass of the composition of the present invention.
  • composition of the present invention may further contain inorganic particles for the purpose of improving the optical properties, workability, mechanical properties, and physicochemical properties of the cured product.
  • the kind of inorganic particles to be blended may be selected according to the purpose, or a single kind may be blended or a plurality of kinds may be blended in combination.
  • the inorganic particles may be surface-treated with a surface treatment agent such as a silane coupling agent.
  • inorganic oxide particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, silicon nitride, boron nitride, silicon carbide, nitride
  • inorganic oxide particles such as silica, barium titanate, titanium oxide, zirconium oxide, niobium oxide, aluminum oxide, cerium oxide, yttrium oxide, silicon nitride, boron nitride, silicon carbide, nitride
  • nitride particles such as aluminum, carbon compound particles, and diamond particles, but other materials can be selected according to the purpose, and the present invention is not limited thereto.
  • the form of the inorganic particles to be blended may be any form such as powder or slurry depending on the purpose.
  • the average particle size of the inorganic particles to be blended is not particularly limited, and those having an average particle size according to the purpose are used. Usually, it is about 1/10 or less of the particle
  • the particle diameter is a value obtained by measuring the minor axis and major axis of the particle by SEM (scanning electron microscope) observation and calculating (minor axis + major axis) / 2. This operation is performed on the particles in a fixed section in the SEM image, and the arithmetic average value of the obtained particle diameters is taken as the average particle diameter of the inorganic particles.
  • the blending amount of the inorganic particles is arbitrary as long as the characteristics such as heat-resistant transparency of the cured product of the present invention are not impaired. If the blended amount of inorganic particles is too small, the desired effect may not be obtained, and if it is too large, it may adversely affect various properties such as heat-resistant transparency, adhesion, transparency, moldability, and hardness of the cured product. is there. It may be 1 to 50% by mass, preferably 5 to 35% by mass, based on the total mass of the composition of the present invention.
  • composition of the present invention includes a mold release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, and the like within a range that does not impair characteristics such as transparency of the cured product You may mix
  • the composition of this invention can be prepared by mix
  • the mixing method is not particularly limited. For example, a mixing method such as a universal kneader or a kneader can be employed. Moreover, you may mix (C) component with (A) component or (B) component previously.
  • (A) component and (C) component are preserve
  • the second composition containing the remainder of component (B) and component (A) may be stored in separate containers and mixed immediately before use to form the composition of the present invention.
  • the composition of the present invention thus prepared may be used as it is, or may be used after degassing under reduced pressure.
  • the cured product of the present invention is obtained by curing the composition of the present invention.
  • the cured product of the present invention can be used as a sealing material for semiconductor devices, and is particularly suitable as a sealing material for optical semiconductor devices and power semiconductor devices.
  • a sealing material for optical semiconductor devices it can be suitably used as a sealing material for LED optical members, a sealing material for optical members for semiconductor lasers, etc., among others, as a sealing material for LED optical members. Particularly preferred.
  • optical semiconductor devices have their light extraction efficiency enhanced by various technologies.
  • the transparency of the sealing material of the optical semiconductor element is low, the sealing material absorbs light.
  • the light extraction efficiency of the optical semiconductor device used decreases. As a result, it tends to be difficult to obtain a high-brightness optical semiconductor device product.
  • the energy corresponding to the decrease in light extraction efficiency is changed to heat, which causes thermal deterioration of the optical semiconductor device, which is not preferable.
  • the cured product of the present invention is excellent in transparency. Specifically, the cured product of the present invention has a good light transmittance at a wavelength in the range of usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm or less. Therefore, it is preferable to use the cured product of the present invention as the sealing material in an optical semiconductor device having an emission wavelength in this region because a high-luminance optical semiconductor device can be obtained. In addition, this does not prevent using the hardened
  • the light transmittance can be measured by measuring transmittance with an ultraviolet / visible spectrophotometer.
  • the cured product of the present invention is excellent in heat-resistant transparency. That is, the cured product of the present invention has a property that the transmittance with respect to light having a predetermined wavelength does not easily fluctuate even when left for a long time under high temperature conditions. Specifically, the cured product of the present invention has a transmittance for light having a wavelength in the region of usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm or less before and after being left to stand at 200 ° C. for 100 hours. Has a good retention rate.
  • the cured product of the present invention as an encapsulant for an optical semiconductor device having an emission wavelength in this region because a high-intensity optical semiconductor device can be obtained and heat deterioration hardly occurs.
  • this does not prevent using the hardened
  • the variation ratio of the transmittance can be measured by measuring the transmittance with an ultraviolet / visible spectrophotometer.
  • the method for producing the cured product of the present invention is to cure the composition of the present invention, and other conditions are not particularly limited.
  • This curing may be performed by heating the composition of the present invention, may be heated at 45 to 300 ° C, and is preferably heated at 60 to 200 ° C. Within this range, it is practical that adhesiveness and foaming are hardly observed in the resulting cured product.
  • the heating time is not particularly limited, but may be about 0.5 to 12 hours, and preferably about 1 to 10 hours. If the heating time is 0.5 hours or longer, curing proceeds sufficiently, but if accuracy is required, such as for LED sealing, it is preferable to lengthen the curing time.
  • the cured product of the present invention may be a cured product obtained by molding the composition of the present invention.
  • This molding method is not particularly limited.
  • the composition of the present invention is combined with an object to be sealed such as an LED by a method such as injection, dripping, casting, casting, extrusion from a container, or integral molding by transfer molding or injection molding at a desired site. By heating, the composition can be cured to obtain a cured product, and the object to be sealed can be sealed.
  • the cured product of the present invention can be used as a sealing material for semiconductor devices, and is particularly suitable as a sealing material for optical semiconductor devices and power semiconductor devices.
  • the sealing material made of the cured product of the present invention is excellent in heat-resistant transparency as described above. Moreover, it is excellent in heat resistance, cold resistance, and electrical insulation similarly to the cured
  • the optical semiconductor device of the present invention is an optical semiconductor device including at least an optical semiconductor element, and the optical semiconductor element is sealed at least by the cured product of the present invention.
  • Other configurations of the optical semiconductor device of the present invention are not particularly limited, and members other than the optical semiconductor element may be provided. Examples of such members include a base substrate, lead-out wiring, wire wiring, control element, insulating substrate, reflecting material, heat sink, conductive member, die bonding material, bonding pad, and the like. Further, in addition to the optical semiconductor element, a part or all of the members may be sealed with the cured product of the present invention.
  • optical semiconductor device of the present invention include, but are not limited to, a light emitting diode (LED) device, a semiconductor laser device, and a photocoupler.
  • the optical semiconductor device of the present invention includes, for example, a backlight such as a liquid crystal display, a light source such as illumination, various sensors, a printer and a copier, a measurement light source for a vehicle, a signal light, a display light, a display device, and a light source for a planar light emitter. It is suitably used for displays, decorations, various lights and switching elements.
  • the optical semiconductor device 10 includes at least a sealing material 1, an optical semiconductor element 2, and a bonding wire 3 on an optical semiconductor substrate 6.
  • the optical semiconductor substrate 6 has a recess composed of a bottom surface made of the lead frame 5 and an inner peripheral side surface made of the reflector 4.
  • the optical semiconductor element 2 is connected to the lead frame 5 using a die bond material (not shown).
  • a bonding pad (not shown) provided in the optical semiconductor element 2 and the lead frame 5 are electrically connected by a bonding wire 3.
  • the reflective material 4 has a function of reflecting light from the optical semiconductor element 2 in a predetermined direction.
  • a sealing material 1 is filled in the region of the concave portion of the optical semiconductor substrate 6 so as to at least seal the optical semiconductor element 2. At this time, the sealing material 1 may be filled so as to also seal the bonding wire 3.
  • the sealing material 1 consists of the hardened
  • the phosphor (not shown) may be included in the sealing material 1.
  • the sealing material 1 can protect the optical semiconductor element 2 from moisture, dust, and the like, and can maintain reliability over a long period of time. Furthermore, since the sealing material 1 also seals the bonding wire 3, it is possible to prevent electrical problems caused by the bonding wire 3 being disconnected, cut, or short-circuited at the same time.
  • the cured product of the present invention can be used as an adhesive for semiconductors as described later. Therefore, it can also be employed as the above-described die bond material.
  • the optical semiconductor element 2 sealed with the sealing material 1 made of the cured product of the present invention for example, an LED, a semiconductor laser, a photodiode, a phototransistor, a solar cell, a CCD (charge coupled device). Etc.
  • the structure shown in FIG. 1 is only an example of the optical semiconductor device of the present invention, and the structure of the reflector, the structure of the lead frame, the mounting structure of the optical semiconductor element, and the like can be modified as appropriate.
  • the method for manufacturing the optical semiconductor device 10 shown in FIG. 1 is not particularly limited.
  • the optical semiconductor element 2 is die-bonded to a lead frame 5 provided with a reflective material 4, the optical semiconductor element 2 and the lead frame 5 are wire-bonded by a bonding wire 3, and then provided around the optical semiconductor element.
  • An example is a method in which the composition of the present invention is filled on the inner side of the reflecting material (the recess made of the lead frame and the reflecting material), and then cured by heating at 50 to 250 ° C. to obtain the sealing material 1.
  • the composition of the present invention Since the composition of the present invention has good adhesion, it can be used as an adhesive for semiconductor 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 device and an external optical member, etc.
  • the composition of the invention can be used by coating, printing, potting and the like. Since the composition of the present invention is excellent in heat resistance, it provides a highly reliable optical semiconductor device that can withstand long-term use when used as an adhesive for high-power optical semiconductor devices exposed to high temperatures and ultraviolet light for a long time. can do.
  • the sample was measured by 1 H-NMR, and the ratio of the proton of dimethyl sulfoxide and the proton of the functional group (H—Si group or CH 2 ⁇ CH—Si group) was calculated, and the functional group in the measurement sample The number of moles was determined.
  • a nuclear magnetic resonance apparatus manufactured by JEOL Ltd., model number: ECA-400 having a resonance frequency of 400 MHz was used.
  • the mass average molecular weight (Mw) of the synthesized silicone resin was calculated by creating a calibration curve using polystyrene as a reference substance by the gel permeation chromatography (abbreviation: GPC) method under the following conditions: Apparatus: HLC-8320GPC (trade name; manufactured by Tosoh Corporation), Column: TSK gel Super HZ 2000x4, 3000x2 (trade name; manufactured by Tosoh Corporation), Eluent: tetrahydrofuran.
  • GPC gel permeation chromatography
  • the viscosity of the synthesized silicone resin is measured using a rotational viscometer (Brookfield Engineering Laboratories Inc., product name: DV-II + PRO) and a temperature control unit (Brookfield Engineering Laboratories Inc., product name: THERMOSEL). , Measured at 25 ° C. The viscosity of silicone resins 1-3 and 1-5 described later was measured at 50 ° C.
  • silicone resin (1-1) When toluene was distilled off from the organic layer under reduced pressure using an evaporator, 192 g of silicone resin (1-1) was obtained as a colorless viscous liquid.
  • the silicone resin (1-1) has a mass average molecular weight (Mw) of 7,100, a refractive index of 1.5115, a viscosity of 520,000 cP, and a CH 2 ⁇ CH—Si group content of 0.
  • the content of HO—Si group was 1.4 mmol / g.
  • the silicone resin (1-2) has a mass average molecular weight (Mw) of 860, a refractive index of 1.5019, a viscosity of 2,900 cP, and a CH 2 ⁇ CH—Si group content of 0.73 mmol. / G, and the HO—Si group content was 7.8 mmol / g.
  • reaction was carried out by stirring for 4 hours at 40 ° C. Thereafter, the reaction solution was returned to room temperature and transferred to a 1 L separatory funnel. After adding 300 g of 3% by mass hydrochloric acid to the separatory funnel and stirring, the upper organic layer of the reaction solution separated into two layers was recovered. The same operation was repeated three times and then washed with 300 mL of water. When toluene was distilled off from the organic layer under reduced pressure using an evaporator, 61.52 g of silicone resin (1-5) was obtained as a colorless viscous liquid.
  • the silicone resin (1-5) has a mass average molecular weight (Mw) of 4,000, a refractive index of 1.5104, a viscosity of 310,000 cP, and a CH 2 ⁇ CH—Si group content of 0.
  • the HO—Si group content was 1.1 mmol / g.
  • reaction solution was returned to room temperature, transferred to a 2 L separatory funnel, 400 mL of toluene and 400 mL of water were added, and after performing a liquid separation operation, the aqueous layer was removed.
  • the organic layer was washed twice with 400 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure using an evaporator to obtain 160.8 g of a silicone resin (2-1) as a colorless viscous liquid.
  • the mass average molecular weight (Mw) of the silicone resin (2-1) is 1,200, the composition ratio is (Me 2 SiO 2/2 ) 0.49 (PhSiO 3/2 ) 0.51 , and the content of HO—Si group was 6.1 mmol / g (9.0 mass%).
  • Synthesis Example 2-2 1,000 g of a silicone resin prepared by repeating the same operation as in Synthesis Example 2-1 was collected in a 2 L-4 neck flask equipped with a fluororesin stirring blade, Dean Stark, and Dimroth type reflux condenser. Next, 250 g of toluene was added, and the inside of the flask was continuously heated at 130 ° C. for 24 hours to conduct hydrolysis and condensation reactions. Thereafter, the reaction solution was returned to room temperature to prepare a silicone resin (2-2) containing toluene.
  • the mass average molecular weight (Mw) of the silicone resin (2-2) is 3,400, the composition ratio is (Me 2 SiO 2/2 ) 0.49 (PhSiO 3/2 ) 0.51 , and the content of HO—Si group was 4.9 mmol / g (7.5 mass%), and the toluene content was 11.4 mass%.
  • silicone resin (2-3) has a mass average molecular weight (Mw) of 4,000, a viscosity of 1,700 cP, and a composition ratio of (Me 2 SiO 2/2 ) 0.36 (PhSiO 3/2 ) 0.46 (H (Me) 2 SiO 1/2 ) 0.18 , the H—Si group content is 1.58 mmol / g, and the HO—Si group content is 2.4 mmol / g (4.0% by mass). there were.
  • Mw mass average molecular weight
  • Respective physical property values (content of H—Si group or CH 2 ⁇ CH—Si group, HO— in silicone resins (1-1) to (1-5) and silicone resins (2-1) to (2-3)
  • Table 2 shows the Si group content, mass average molecular weight, refractive index, and viscosity.
  • the Vi—Si group represents a CH 2 ⁇ CH—Si group, and “—” represents that it has not been measured.
  • Examples 1-2 and Comparative Examples 1-3 The synthesized silicone resins (1-1) to (1-5) and the silicone resin (2-3) are blended so that the molar ratio of CH 2 ⁇ CH—Si groups to H—Si groups is 1: 2. Then, a platinum catalyst was mixed as a hydrosilylation catalyst to prepare curable compositions (Compositions 1-2 and Comparative compositions 1-3), respectively.
  • the platinum catalyst is platinum (0) -1,3-divinyl-1,1,3,3 so that the content of platinum atoms is 1 ppm by mass with respect to the total amount of the curable composition. -Tetramethyldisiloxane complex was used. Table 3 summarizes the prepared curable compositions.
  • a mixture of the prepared curable composition and zirconia balls having a diameter of 50 ⁇ m is potted on a glass substrate (50 mm ⁇ 50 mm ⁇ 3.0 mm) or an alumina substrate (50 mm ⁇ 50 mm ⁇ 2.0 mm), and glass A chip (5.0 mm ⁇ 5.0 mm ⁇ 1.1 mm) is placed on the potted composition, heated in air at 90 ° C. for 1 hour in a sandwiched state, and further heated at 150 ° C. for 4 hours to effect the curing.
  • the specimen was prepared by curing the adhesive composition. Similarly, a total of 10 specimens were produced.
  • the adhesive strength (adhesive strength) of each specimen was measured with a bond tester (manufactured by Daisy Japan Co., Ltd., model: Dage4000Plus), and the average value of the adhesive strength of 10 specimens was calculated.
  • Example 1 As shown in Table 3, foaming and cracking of the cured product were not confirmed in all of Examples 1 and 2 and Comparative Examples 1 to 3, but tackiness of the cured product was observed in Comparative Examples 1 to 3. It was. The cured product of Example 1 was particularly good without tackiness.
  • Example 1 obtained the highest values.
  • Comparative Examples 1 and 3 the cured product was very fragile, and the elastic modulus, stress at break, and strain at break could not be measured.
  • Shore hardness in Examples 1-2 and Comparative Examples 1-3, the hardest cured product in Example 1 was obtained.
  • Example 1 From the above, the cured product obtained in Example 1 showed no foaming or cracking, no tackiness, and excellent mechanical strength.

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Abstract

La présente invention décrit une composition de résine de silicone durcissable contenant au moins une première résine de silicone qui est obtenue par hydrolyse-polycondensation d'une première composition d'alcoxysilane et présente un poids moléculaire moyen en masse de 3 800 à 20 000, une seconde résine de silicone qui possède un groupe Si-H, et un catalyseur d'hydrosilylation. La composition d'alcoxysilane contient au moins divers composés oxysilane représentés par les formules générales (1) à (3). Cette composition de résine de silicone durcissable est susceptible de fournir un matériau d'étanchéité pour dispositifs semi-conducteurs optiques, qui ne contient pas de bulles d'air et est exempt de collant. R1Si(OR2)3 [1] R3 2Si(OR4)2 [2] CH2=CH-Si(OR5)3 [3]
PCT/JP2016/076543 2015-09-29 2016-09-09 Composition de résine de silicone durcissable, son produit durci, et dispositif semi-conducteur optique utilisant ledit produit durci WO2017056913A1 (fr)

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Cited By (1)

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CN115803366A (zh) * 2020-07-10 2023-03-14 Ams-欧司朗国际有限公司 用于制备聚硅氧烷的前体、聚硅氧烷、聚硅氧烷树脂、用于制备聚硅氧烷的方法、用于制备聚硅氧烷树脂的方法以及光电子器件

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Publication number Priority date Publication date Assignee Title
WO2011162294A1 (fr) * 2010-06-24 2011-12-29 積水化学工業株式会社 Agent de scellement pour dispositif à semi-conducteurs optique, et dispositif à semi-conducteurs optique mettant en œuvre celui-ci
WO2013021717A1 (fr) * 2011-08-10 2013-02-14 株式会社Adeka Composition durcissable contenant du silicium et produit durci à base de celle-ci
JP2013253210A (ja) * 2012-06-08 2013-12-19 Sekisui Chem Co Ltd 光半導体装置用硬化性組成物、光半導体装置及び光半導体装置の製造方法
JP2014196462A (ja) * 2013-03-07 2014-10-16 Jsr株式会社 硬化性組成物、硬化物および光半導体装置

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WO2011162294A1 (fr) * 2010-06-24 2011-12-29 積水化学工業株式会社 Agent de scellement pour dispositif à semi-conducteurs optique, et dispositif à semi-conducteurs optique mettant en œuvre celui-ci
WO2013021717A1 (fr) * 2011-08-10 2013-02-14 株式会社Adeka Composition durcissable contenant du silicium et produit durci à base de celle-ci
JP2013253210A (ja) * 2012-06-08 2013-12-19 Sekisui Chem Co Ltd 光半導体装置用硬化性組成物、光半導体装置及び光半導体装置の製造方法
JP2014196462A (ja) * 2013-03-07 2014-10-16 Jsr株式会社 硬化性組成物、硬化物および光半導体装置

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115803366A (zh) * 2020-07-10 2023-03-14 Ams-欧司朗国际有限公司 用于制备聚硅氧烷的前体、聚硅氧烷、聚硅氧烷树脂、用于制备聚硅氧烷的方法、用于制备聚硅氧烷树脂的方法以及光电子器件
CN115803366B (zh) * 2020-07-10 2024-02-09 Ams-欧司朗国际有限公司 制备聚硅氧烷的前体、聚硅氧烷及其制备方法、聚硅氧烷树脂及其制备方法和光电子器件

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