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WO2016013421A1 - Composition de résine de silicone durcissable, objet durci obtenu à partir de celle-ci, et dispositif optique semi-conducteur formé au moyen de celui-ci - Google Patents

Composition de résine de silicone durcissable, objet durci obtenu à partir de celle-ci, et dispositif optique semi-conducteur formé au moyen de celui-ci Download PDF

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Publication number
WO2016013421A1
WO2016013421A1 PCT/JP2015/069877 JP2015069877W WO2016013421A1 WO 2016013421 A1 WO2016013421 A1 WO 2016013421A1 JP 2015069877 W JP2015069877 W JP 2015069877W WO 2016013421 A1 WO2016013421 A1 WO 2016013421A1
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Prior art keywords
silicone resin
component
group
composition
resin composition
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PCT/JP2015/069877
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English (en)
Japanese (ja)
Inventor
亘 河合
勝宏 秋山
佑 松野
惇也 中辻
真 情野
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Central Glass Co Ltd
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Central Glass Co Ltd
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Priority claimed from JP2015131140A external-priority patent/JP2016169358A/ja
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to CN201580041251.7A priority Critical patent/CN106574118A/zh
Priority to KR1020177003741A priority patent/KR20170032362A/ko
Priority to US15/328,067 priority patent/US20170218128A1/en
Publication of WO2016013421A1 publication Critical patent/WO2016013421A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/852—Encapsulations
    • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins
    • H10W74/10—
    • H10W74/40—

Definitions

  • the present invention relates to a curable silicone resin composition that can be suitably used as a raw material for a sealing material of an optical semiconductor element such as a light emitting diode, a raw material for an adhesive, a cured product thereof, and an optical semiconductor device using these.
  • 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 SiH group and an alkenyl group as a material for protecting and sealing an optical device or a semiconductor device. .
  • silicone resin compositions contain a platinum-based metal catalyst, particularly a platinum catalyst, as a curing catalyst.
  • a silicone resin composition containing a platinum catalyst may turn yellow when exposed to a high temperature for a long time.
  • a cured product of a silicone resin composition containing a platinum catalyst has a problem that transparency is impaired when exposed to a high temperature for a long time.
  • a silicone resin that solves such problems and has sufficient transparency even when exposed to high temperatures for a long period of time that is, a silicone resin that provides a cured product excellent in heat-resistant transparency Development of compositions is desired.
  • the present invention has been made in view of the above circumstances, and provides an addition-curable curable silicone resin composition that provides a cured product having excellent heat-resistant transparency, a cured product thereof, and an optical semiconductor device using these. With the goal.
  • component a silicone resin represented by the following formula [1] and containing a hydrogen atom (SiH group) bonded to a silicon atom;
  • Component (B): it is represented by the following formula [2], a silicone resin containing a vinyl group bonded to a silicon atom (Si-CH CH 2 groups), and component (C): wherein at least a platinum catalyst,
  • the total content of silanol groups (Si—OH groups) in component (B) and component (B) is 0.5 to 5.0 mmol / g, and the content of platinum atoms in component (C) is (A)
  • a curable silicone resin composition having a mass unit of 0.003 to 3.0 ppm with respect to the total mass of the component, the component (B) and the component (C), It came to complete the addition-curable type curable silicone resin composition excellent in heat
  • R 1 is an alkyl group having 1 to 3 carbon atoms
  • R 2 is an alkyl group having 1 to 3 carbon atoms
  • R 2 may be the same or different from each other
  • R 3 is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • the oxygen atom in the structural unit represented by each represents an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group.
  • R 4 is an alkyl group having 1 to 3 carbon atoms
  • two R 4 may be the same or different from each other
  • R 4 is an alkyl group having 1 to 3
  • the present invention includes the following invention 1 to invention 15.
  • the total content of silanol groups (Si—OH groups) in component (B) and component (B) is 0.5 to 5.0 mmol / g, and the content of platinum atoms in component (C) is
  • a curable silicone resin composition having a mass unit of 0.003 to 3.0 ppm based on the total mass of the component, the component (B), and the component (C).
  • R 1 is an alkyl group having 1 to 3 carbon atoms
  • R 2 is an alkyl group having 1 to 3 carbon atoms
  • R 2 may be the same or different from each other
  • R 3 is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • the oxygen atom in the structural unit represented by each represents an oxygen atom forming a siloxane bond or an oxygen atom forming a silanol group.
  • R 4 is an alkyl group having 1 to 3 carbon atoms
  • two R 4 may be the same or different from each other
  • R 4 is an alkyl group having 1 to 3
  • invention 8 The curable silicone resin composition according to any one of Inventions 1 to 7, further comprising one or more selected from the group consisting of an adhesion-imparting agent, a phosphor and inorganic particles.
  • invention 9 Curing according to any one of inventions 1 to 8, further comprising at least one selected from the group consisting of a mold release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, a leveling agent, and an anti-sagging agent. Silicone resin composition.
  • a sealing material comprising a cured product of the curable silicone resin composition according to any one of inventions 1 to 9.
  • invention 12 A method for producing a cured product of a curable silicone resin composition, wherein the curable silicone resin composition according to any one of Inventions 1 to 9 is heated and cured at 45 ° C or higher and 300 ° C or lower.
  • invention 14 The adhesive for semiconductors which consists of a hardened
  • alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms may be a substituted or unsubstituted aromatic hydrocarbon group, and some or all of the hydrogen atoms may be substituted with fluorine atoms.
  • Specific examples include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, and a 3,5-di (trifluoromethylphenyl) group.
  • FIG. 2 is a graph showing the relationship between the shear viscosity and the temperature of compositions prepared in Examples and Comparative Examples (Composition 1-1 to Composition 1-5, Comparative Composition 1-1).
  • FIG. 4 is a graph showing the relationship between the shear viscosity and the temperature of compositions prepared in Examples and Comparative Examples (Composition 4-1 to Composition 4-3, Comparative Composition 4-1).
  • FIG. 3 is a graph showing the relationship between shear viscosity and time of compositions prepared in Examples (Composition 1-1, Composition 1-6 to Composition 1-9).
  • the curable silicone resin composition of the present invention contains at least a predetermined amount of the components (A) to (C), and the composition is heated.
  • the cured product thus obtained is suitably used as a sealing material for optical semiconductor devices.
  • each component contained in the composition of this invention is demonstrated.
  • the component (A) is a silicone resin represented by the following formula [1] and containing a hydrogen atom (SiH group) bonded to a silicon atom.
  • the above formula [1] represents an average composition formula.
  • R 1 is an alkyl group having 1 to 3 carbon atoms, and two R 1 may be the same or different from each other.
  • R 2 is an alkyl group having 1 to 3 carbon atoms, and the two R 2 may be the same or different from each other.
  • R 3 is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • the oxygen atom in the structural unit represented by (SiR 2 2 O 2/2 ), (R 3 SiO 3/2 ) and (SiO 4/2 ) is an oxygen atom or silanol group forming a siloxane bond, respectively. The oxygen atom which forms is shown.
  • alkyl group having 1 to 3 carbon atoms in R 1 a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
  • alkyl group having 1 to 3 carbon atoms in R 2 a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
  • alkyl group having 1 to 3 carbon atoms in R 3 a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms in R 3 is preferably a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group.
  • a phenyl group is particularly preferred.
  • R 1 , R 2 and R 3 are not particularly limited. Among them, R 1 is a methyl group or an ethyl group, R 2 is a methyl group or an ethyl group, R 3 is a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or 3, It is preferably any one of 5-di (trifluoromethylphenyl) groups, particularly preferably R 1 is a methyl group, R 2 is a methyl group, and R 3 is a phenyl group.
  • the value of a is preferably 0.05 to 0.40, particularly preferably 0.20 to 0.40. If the value of a is 0.05 or more, the composition of the present invention has good moldability, and if it is 0.40 or less, the cured product of the present invention has good mechanical strength.
  • the value of b is preferably 0.10 to 0.80, particularly preferably 0.10 to 0.40. If the value of b is 0.10 or more, the composition of the present invention has good moldability, and if it is 0.80 or less, the cured product of the present invention has good mechanical strength.
  • the value of c is preferably 0.10 to 0.80, particularly preferably 0.30 to 0.60. If the value of c is 0.10 or more, the cured product of the present invention has good mechanical strength, and if it is 0.80 or less, the composition of the present invention has good moldability.
  • the value of d is preferably 0 to 0.70.
  • the value of d is particularly preferably 0.10 to 0.30 since the cured product of the present invention exhibits good adhesive strength and good hardness.
  • the value of d is 0, there is no structural unit of (SiO 4/2 ) in the above formula [1].
  • a, b, c and d should be calculated by measuring the 29 Si-NMR spectrum and 1 H-NMR spectrum of component (A) using a nuclear magnetic resonance apparatus and using these in a complementary combination. Can do.
  • the structural unit represented by (SiR 2 2 O 2/2 ) is a structure represented by the following formula [1-2], that is, represented by (SiR 2 2 O 2/2 ).
  • the structure unit may include a structure in which one of oxygen atoms bonded to a silicon atom forms a silanol group.
  • R 2 has the same meaning as R 2 in the formula [1]
  • X represents a hydroxy group.
  • the structural unit represented by (SiR 2 2 O 2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-b], and further includes the following formula [1-2-b]
  • the part enclosed with the broken line of the structural unit represented by may be included. That is, a structural unit having a group represented by R 2 and having a hydroxy group remaining at the terminal to form a silanol group is also included in the structural unit represented by (SiR 2 2 O 2/2 ). It is.
  • the oxygen atom in the Si—O—Si bond forms a siloxane bond with an adjacent silicon atom, It shares an oxygen atom with an adjacent structural unit.
  • one oxygen atom in the Si—O—Si bond is defined as “O 1/2 ”.
  • R 2 has the same meaning as R 2 in the formula [1].
  • X represents a hydroxy group.
  • the structural unit represented by (R 3 SiO 3/2 ) is a structure represented by the following formula [1-3] or [1-4], that is, a structure represented by (R 3 SiO 3/2 ).
  • the structure which forms the silanol group may be included.
  • R 3 has the same meaning as R 3 in the formula [1]
  • X represents a hydroxy group.
  • the structural unit represented by (R 3 SiO 3/2) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-c], and further represented by the following formula [1-3-c] or A portion surrounded by a broken line of the structural unit represented by [1-4-c] may be included. That is, a structural unit having a group represented by R 3 and having a hydroxy group remaining at the terminal to form a silanol group is also included in the structural unit represented by (R 3 SiO 3/2 ). .
  • the formula [1-c], R 3 in [1-3-c] and [1-4-c] has the same meaning as R 3 in the formula [1].
  • X represents a hydroxy group.
  • the structural unit represented by (SiO 4/2 ) is a structure represented by the following formula [1-5], [1-6] or [1-7], that is, (SiO 4/2 ) a structure in which three or two oxygen atoms bonded to a silicon atom in the structural unit represented by each form a silanol group, or in a structural unit represented by (SiO 4/2 ) A structure in which one of oxygen atoms bonded to a silicon atom forms a silanol group may be included.
  • X represents a hydroxy group.
  • the structural unit represented by (SiO 4/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-d], and further includes the following formulas [1-5-d], [1 A portion surrounded by a broken line of the structural unit represented by ⁇ 6 ⁇ d] or [1-7-d] may be included. That is, a structural unit in which a hydroxy group remains at the terminal to form a silanol group is also included in the structural unit represented by (SiO 4/2 ). In the above formulas [1-5-d], [1-6-d] and [1-7-d], X represents a hydroxy group.
  • the component (A) contains at least hydrogen atoms (SiH groups) bonded to silicon atoms, and the number thereof is not particularly limited. It is preferable to contain 2 or more in one molecule. In order to obtain a good cured product, the content of hydrogen atoms (SiH groups) bonded to silicon atoms in the component (A) is particularly preferably 1.0 mmol / g to 4.0 mmol / g.
  • the mass average molecular weight is a value obtained by measurement by a gel permeation chromatography (abbreviation: GPC) method and conversion by a standard polystyrene calibration curve (the same applies hereinafter).
  • GPC gel permeation chromatography
  • the viscosity of the component (A) is not particularly limited. From the viewpoint of handling workability, the viscosity at 25 ° C. is preferably 0.001 to 10,000,000 cP (centipoise), more preferably 0.01 to 500,000 cP. If the viscosity is more than 10,000,000 cP, the moldability may be inferior, but it is also possible to treat the temperature by heating.
  • the viscosity of the component (A) can be measured by a rotational viscometer or the like.
  • the amount of Si—OH group contained in the component (A) is not particularly limited. 0.5 to 4.5 mmol / g is preferable, and 1.0 to 3.5 mmol / g is particularly preferable. If the Si—OH group content exceeds 4.5 mmol / g, bubbles may be observed in the cured product.
  • Component (B) is a silicone resin represented by the following formula [2] and containing a vinyl group (Si—CH ⁇ CH 2 group) bonded to a silicon atom.
  • component (B) only one type may be used, or two or more types may be used in combination.
  • the above formula [2] represents an average composition formula.
  • R 4 is an alkyl group having 1 to 3 carbon atoms, and the two R 4 may be the same or different.
  • R 5 is an alkyl group having 1 to 3 carbon atoms, and the two R 5 may be the same or different.
  • R 6 is an alkyl group having 1 to 3 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • Each of e, f, and g is a number in the range of more than 0 and less than 1
  • h is a number in the range of 0 to less than 1
  • e + f + g + h 1.
  • the oxygen atoms in the structural units represented by (SiR 5 2 O 2/2 ), (R 6 SiO 3/2 ) and (SiO 4/2 ) are each an oxygen atom forming a siloxane bond or a silanol group The oxygen atom which forms is shown.
  • alkyl group having 1 to 3 carbon atoms in R 4 a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
  • alkyl group having 1 to 3 carbon atoms in R 5 a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
  • alkyl group having 1 to 3 carbon atoms in R 6 a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms in R 6 is preferably a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or a 3,5-di (trifluoromethylphenyl) group.
  • a phenyl group is particularly preferred.
  • R 4 is a methyl group or an ethyl group
  • R 5 is a methyl group or an ethyl group
  • R 6 is a methyl group, an ethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, or 3
  • It is preferably any one of 5-di (trifluoromethylphenyl) groups, particularly preferably R 4 is a methyl group, R 5 is a methyl group, and R 6 is a methyl group or a phenyl group.
  • the value of e is preferably 0.05 to 0.40, particularly preferably 0.15 to 0.30. If the value of e is 0.05 or more, the composition of the present invention has good moldability, and if it is 0.40 or less, the cured product of the present invention has good mechanical strength.
  • the value of f is preferably 0.10 to 0.80, particularly preferably 0.20 to 0.70. If the value of f is 0.10 or more, the composition of the present invention has good moldability, and if it is 0.80 or less, the cured product of the present invention has good mechanical strength.
  • the value of g is preferably 0.10 to 0.80, particularly preferably 0.20 to 0.70. If the value of g is 0.10 or more, the cured product of the present invention has good mechanical strength, and if it is 0.80 or less, the composition of the present invention has good moldability.
  • the value of h is preferably 0 to 0.70.
  • the value of h is particularly preferably 0.10 to 0.30 since the cured product of the present invention exhibits good adhesive strength and good hardness.
  • the value of h is 0, there is no structural unit of (SiO 4/2 ) in the above formula [2].
  • e, f, g, and h are calculated by measuring the 29 Si-NMR spectrum and 1 H-NMR spectrum of component (B) using a nuclear magnetic resonance apparatus, and using these in a complementary combination. Can do.
  • the structural unit represented by (SiR 5 2 O 2/2 ) is a structure represented by the following formula [2-2], that is, represented by (SiR 5 2 O 2/2 ).
  • the structure unit may include a structure in which one of oxygen atoms bonded to a silicon atom forms a silanol group.
  • R 5 has the same meaning as R 5 in the formula [2]
  • X represents a hydroxy group.
  • the structural unit represented by (SiR 5 2 O 2/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [2-b], and further includes the following formula [2-2-2-b]
  • the part enclosed with the broken line of the structural unit represented by may be included. That is, a structural unit having a group represented by R 5 and having a hydroxy group remaining at the terminal to form a silanol group is also included in the structural unit represented by (SiR 5 2 O 2/2 ). It is.
  • the oxygen atom in the Si—O—Si bond forms a siloxane bond with an adjacent silicon atom, It shares an oxygen atom with an adjacent structural unit.
  • one oxygen atom in the Si—O—Si bond is defined as “O 1/2 ”.
  • R 5 are the same as R 5 in the formula [2].
  • X represents a hydroxy group.
  • the structural unit represented by (R 6 SiO 3/2 ) is a structure represented by the following formula [2-3] or [2-4], that is, (R 6 SiO 3 / 2 ) A structure in which two of the oxygen atoms bonded to the silicon atom in the structural unit represented by each form a silanol group, or a silicon atom in the structural unit represented by (R 6 SiO 3/2 ) A structure in which one of the bonded oxygen atoms forms a silanol group may be included.
  • R 6 has the same meaning as R 6 in the formula [2]
  • X represents a hydroxy group.
  • the structural unit represented by (R 6 SiO 3/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [2-c], and further includes the following formula [2-3-c] or A portion surrounded by a broken line of the structural unit represented by [2-4-c] may be included. That is, a structural unit having a group represented by R 6 and having a hydroxy group remaining at the terminal to form a silanol group is also included in the structural unit represented by (R 6 SiO 3/2 ). .
  • the formula [2-c], in [2-3-c] and [2-4-c], R 6 has the same meaning as R 6 in the formula [2]. In the above formulas [2-3-c] and [2-4-c], X represents a hydroxy group.
  • the structural unit represented by (SiO 4/2 ) is represented by the following formula [2-5], [2-6] or [2-7], that is, represented by (SiO 4/2 ).
  • One of these may contain a structure in which a silanol group is formed.
  • X represents a hydroxy group.
  • the structural unit represented by (SiO 4/2 ) includes a portion surrounded by a broken line of the structural unit represented by the following formula [2-d], and further includes the following formulas [2-5-d], [2 A portion surrounded by a broken line of the structural unit represented by ⁇ 6 ⁇ d] or [2-7-d] may be included. That is, a structural unit in which a hydroxy group remains at the terminal to form a silanol group is also included in the structural unit represented by (SiO 4/2 ). In the above formulas [2-5-d], [2-6-d] and [2-7-d], X represents a hydroxy group.
  • the component (B) contains at least a vinyl group (Si—CH ⁇ CH 2 group) bonded to a silicon atom, and the number thereof is not particularly limited. It is preferable to contain 2 or more in one molecule. Since a good cured product can be obtained, the content of the vinyl group (Si—CH ⁇ CH 2 group) bonded to the silicon atom in the component (B) is 0.5 mmol / g to 4.0 mmol / g. Particularly preferred.
  • 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 10,000,000 cP, and more preferably 0.001 to 500,000 cP. If the viscosity is more than 10,000,000 cP, the moldability may be inferior, but it is also possible to treat the temperature by heating.
  • the viscosity of the component (B) can be measured with a rotational viscometer or the like.
  • the amount of Si—OH group contained in the component (B) is not particularly limited.
  • the content of Si—OH groups is preferably 0.5 to 6.0 mmol / g, particularly preferably 1.0 to 3.5 mmol / g. If the Si—OH group content exceeds 6.0 mmol / g, bubbles may be observed in the cured product.
  • ⁇ (C) component The component (C) is blended in order to promote an addition curing reaction between a SiH group in the component (A) and a Si—CH ⁇ CH 2 group in the component (B) described later.
  • a component may be used individually by 1 type, or may use 2 or more types together.
  • the kind of component is not specifically limited. Specifically, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex (cursted catalyst), platinum-cyclovinylmethylsiloxane complex, or platinum-octylaldehyde complex Etc. can be illustrated. Of these, platinum-divinyltetramethyldisiloxane complex (cursed catalyst) and platinum-cyclovinylmethylsiloxane complex are preferable.
  • the composition of the present invention aims to improve the storage stability and handling workability of the composition and to adjust the hydrosilylation reactivity during 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 of the present invention. .
  • the type of curing retarder is not particularly limited as long as it is a compound having a curing retarding effect on the component (C), and conventionally known compounds 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.
  • oxidation retarders compounds containing aliphatic unsaturated bonds and nitrogen-containing compounds are preferred, maleic esters, propargyl alcohols, N, N, N ′, N′-tetrasubstituted alkyldiamines.
  • Dimethyl maleate, 2-methyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, and N, N, N ′, N′-tetramethylethylenediamine are particularly preferred.
  • the content of the curing retarder in the composition of the present invention is not particularly limited. Usually, a curing retarder may be added in an amount of 20 to 200 equivalents per 1 equivalent of platinum atoms in the component (C) contained in the composition, but this is not restrictive.
  • 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.
  • the composition of the present invention can be stored for a long period of time at room temperature (especially an ambient temperature not heated or cooled, usually 15 to 30 ° C., the same applies hereinafter). In addition, the heat curability is excellent.
  • an adhesion-imparting agent may be blended in addition to the components (A) to (C) described above for the purpose of improving the adhesiveness.
  • 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 content of this adhesion-imparting agent in the composition of the present invention is not particularly limited. In the composition of the present invention, it is preferably in the range of 1 to 20% by mass, particularly preferably in the range of 5 to 15% by mass.
  • antioxidants may be 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 phenol-based antioxidants, thioether-based acid additives, and phosphorus-based antioxidants. Of these, phenolic antioxidants and thioether antioxidants are preferred, and thioether antioxidants are particularly preferred. These antioxidants may be used individually by 1 type, and may use 2 or more types together.
  • phenolic antioxidants include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H , 5H) -trione, 4,4 ′, 4 ′-(1-methylpropanyl-3-ylidene) tris (6-tert-butyl-m-cresol, 6,6′-di-tert-butyl-4, 4'-butylidene-di-m-cresol, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], 3,9-bis ⁇ 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethyl este
  • phosphorus antioxidants examples include 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecene, 3,9-bis (2,6 -Di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecene, 2,2'-methylenebis (4,6-di-tert- Butylphenyl) -2-ethylhexyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra-C 12-15 -alkyl (propane-2,2-diylbis ( 4,1-phenylene)) bis (phosphite), 2-ethylhexyl diphenyl phosphit
  • This antioxidant may be a commercially available product or a synthesized product.
  • Commercially available products are ADK STAB (manufactured by Adeka): AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330, AO- Examples thereof include 412S, AO-503, PEP-8, PEP-8W, PEP-36, PEP-36A, HP-10, 2112, 2112RG, 1178, 1500, C, 135A, 3010, and TPP.
  • the blending amount in the case of using this 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. 0.001-2 mass% may be blended with respect to the total mass of the composition of the present invention, and 0.01-1 mass% is preferably blended. If the blending amount is within the above range, the antioxidant ability is sufficiently exhibited, so that a cured product having excellent engineering characteristics can be obtained while suppressing the occurrence of coloring, cloudiness, oxidative degradation, and the like.
  • Conventionally known light stabilizers may be added to the composition of the present invention in order to impart resistance to light degradation caused by light energy such as sunlight and fluorescent lamps.
  • a hindered amine stabilizer that captures radicals generated by photooxidation (photodegradation) is preferably used. By using it together with the above-mentioned antioxidant, the antioxidant effect can be further improved. it can.
  • the light stabilizer examples include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, tetrakis (1,2 , 2,6,6-Pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate Etc.
  • bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is preferable.
  • This light stabilizer may be a commercially available product or a synthesized product.
  • Examples of commercially available products include ADK STAB (manufactured by ADK): LA-77Y, LA-77G, LA-82, and the like.
  • the blending amount in the case of using this 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 blended in an amount of 0.01 to 5% by weight, preferably 0.05 to 0.5% by weight, based on the total weight of the curable silicone resin composition of the present invention.
  • a phosphor may be blended as an optional component.
  • 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.
  • 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.
  • examples include silicate green to yellow light emitting phosphors containing europium ions.
  • the oxynitride phosphor include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions.
  • nitride-based phosphors include calcium, strontium, aluminum, silicon, nitrogen-based casoon-based red light-emitting phosphors including europium ions.
  • sulfides include ZnS-based green color phosphors including copper ions and aluminum ions.
  • oxysulfide phosphor include Y 2 O 2 S red light-emitting phosphor containing europium ions. These phosphors may be used alone or in a mixture of two or more.
  • the amount of the phosphor is not particularly limited. In the composition of the present invention, it is preferably in the range of 10 to 70% by mass, particularly preferably in the range of 20 to 50% by mass.
  • inorganic particles may be blended for the purpose of improving optical properties, workability, mechanical properties, and physicochemical properties in the cured product.
  • the kind of the inorganic particles may be selected according to the purpose, or a single kind may be blended or a plurality of kinds may be blended.
  • the inorganic particles may be surface-treated with a surface treatment agent such as a silane coupling agent.
  • the inorganic particles include 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, and aluminum 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, and aluminum nitride.
  • Nitride particles such as, carbon compound particles, diamond particles, and the like are exemplified, but other materials can be selected according to the purpose, and are not limited thereto.
  • the form of the inorganic particles may be any form depending on the purpose, such as powder or slurry. Depending on the required transparency, it is preferable to make the cured product of the present invention have the same refractive index or blend it into the composition of the present invention as an aqueous / solvent transparent sol.
  • 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 average particle diameter of the inorganic particles means an arithmetic average value when the major axis is measured by selecting any 20 particles from 50 or more particles by observation with a scanning electron microscope (abbreviation: SEM). .
  • 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. About 1 to 50 mass% may be blended, and about 5 to 35 mass% is preferably blended.
  • composition of the present invention has a mold release agent, a resin modifier, a colorant, a diluent, an antibacterial agent, an antifungal agent, and leveling as long as the characteristics such as transparency of the cured product are not impaired.
  • An agent, an anti-sagging agent, and the like may be included.
  • the compounding ratio of the component (A) and the component (B) in the composition of the present invention is not particularly limited. Basically, it is blended based on the molar ratio of the SiH group contained in the molecule of the component (A) and the Si—CH ⁇ CH 2 group contained in the molecule of the component (B). Specifically, the number of moles of SiH groups contained in the molecule of component (A): the number of moles of Si—CH ⁇ CH 2 groups contained in the molecule of component (B) is 0.8: 0. A range of 2 to 0.5: 0.5 is preferable.
  • the composition of the present invention has good moldability, and if it is 0.5 or more, The cured product of the present invention has good heat transparency.
  • the blending amount of the component (C) in the composition of the present invention is such that the platinum atom in the component (C) is 0.00 on a mass basis based on the total mass of the component (A), the component (B), and the component (C).
  • the amount is preferably in the range of 003 to 3.0 ppm, more preferably 0.003 to 2.0 ppm. If the amount of component (C) is 0.003 ppm or more, the addition curing reaction of component (A) and component (B) proceeds smoothly, and if it is 3.0 ppm or less, the resulting cured product is excellent. Since it has heat-resistant transparency, discoloration of the cured product due to long-term heating can be suppressed. Even within the above range, the smaller the amount of the component (C), the more the cured product of the present invention tends to have excellent heat-resistant transparency. Therefore, the smaller the amount of the component (C), the better.
  • the total content of silanol groups (Si—OH groups) in the component (A) and the component (B) in the composition of the present invention may be 0.5 to 5.0 mmol / g, 1.0 to 3.0 mmol / g is preferable, and 1.5 to 3.0 mmol / g is particularly preferable.
  • it exceeds 5.0 mmol / g bubbles may be generated in the cured product produced from the composition. Generation
  • when exceeding 5.0 mmol / g there exists a possibility that hardening of the composition may not fully progress, but a desired hardened
  • the mass average molecular weight is 3,500 to 7,000
  • the mass average molecular weight is 3,500 to 7,000.
  • the total content of silanol groups (Si—OH groups) in the component (A) and the component (B) may be 1.5 to 5.0 mmol / g, and 1.7 to 3.0 mmol. / G is preferred, and 1.9 to 2.7 mmol / g is particularly preferred because a cured product showing excellent adhesion to packages of various sizes can be obtained.
  • the content of silanol groups (Si—OH groups) in the component (A) and the component (B) was determined by measuring the 29 Si-NMR spectrum and 1 H-NMR spectrum for each component using a nuclear magnetic resonance apparatus. Can be calculated using a complementary combination.
  • the viscosity of the composition of the present invention is not particularly limited. From the viewpoint of handling workability, the viscosity at 25 ° C. is preferably 0.001 to 10,000,000 cP, and more preferably 0.001 to 500,000 cP. If the viscosity is more than 10,000,000 cP, the moldability may be inferior, but it is also possible to treat the temperature by heating.
  • the viscosity of the composition of the present invention can be measured with a rotational viscometer or the like.
  • 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 and / or (B) component previously.
  • (B) component and (C) component are preserve
  • the second composition containing the remainder of component A) and component (B) is stored in separate containers, mixed immediately before use to obtain the composition of the present invention, and degassed under reduced pressure for use. May be.
  • the manufacturing method of (A) component is not specifically limited.
  • hydrolysis polycondensation of a dialkoxysilane compound represented by the following general formula [3], a trialkoxysilane compound represented by the general formula [4] and a tetraalkoxysilane compound represented by the general formula [5] A condensate obtained by the reaction (hereinafter sometimes referred to as “hydrolyzed polycondensate [I]”) and the following general formulas [9-1], [9-2], [9-3] or It can be produced by reacting with a silane compound represented by [9-4].
  • R 2 in the general formula [3] has the same meaning as R 2 in the formula [1]
  • R 7 represents an alkyl group having 1 to 3 carbon atoms
  • the two R 7 may be the same or different types from each other Good.
  • R 3 in the general formula [4] has the same meaning as R 3 in the formula [1]
  • R 8 represents an alkyl group having 1 to 3 carbon atoms
  • the three R 8 are the same or different types from each other Also good.
  • R 9 in the general formula [5] represents an alkyl group having 1 to 3 carbon atoms, and the four R 9 may be the same or different from each other.
  • Formula [9-1], [9-2], R 1 in the [9-3] and [9-4] has the same meaning as R 1 in the formula [1].
  • R 13 in the general formula [9-3] represents an alkyl group having 1 to 3 carbon atoms.
  • dialkoxysilane compound represented by the general formula [3] the dialkoxysilane compound represented by the general formula [4]
  • the tetraalkoxysilane compound represented by the general formula [5] are referred to as “dialkoxysilane”, respectively.
  • the silane compounds represented by the general formulas [9-1], [9-2], [9-3] and [9-4] are “chlorosilane compound [9-1]”, “silanol compound [ 9-2] ”,“ monoalkoxysilane compound [9-3] ”, and“ disiloxane compound [9-4] ”. When these are collectively referred to without distinction,“ silane compound [9 ] ".
  • dialkoxysilane [3] include, but are not limited to, the following compounds: Dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane.
  • preferred compounds include dimethyldimethoxysilane and dimethyldiethoxysilane.
  • trialkoxysilane [4] examples include, but are not limited to, the following compounds: Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxy Silane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane, 3,5- (ditrifluoromethyl) phenyltrimethoxy Silane, 3,5- (ditrifluoromethyl) phenyltriethoxysilane, naphthyltrimethoxysilane, naphthyl
  • preferred compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, and 3- (trifluoromethyl) phenyltriethoxysilane.
  • 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane, 3,5- (ditrifluoromethyl) phenyltriethoxy Silanes can be mentioned, and particularly preferable compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
  • tetraalkoxysilane [5] include, but are not limited to, the following compounds: Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane.
  • preferred compounds include tetramethoxysilane and tetraethoxysilane.
  • dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5] used for the production of component (A) is not particularly limited.
  • the dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5] may be used alone or in combination.
  • dialkoxysilane [3] is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and diethyldiethoxysilane, and trialkoxysilane [4] is methyltrimethoxysilane [4].
  • dialkoxysilane [4] is one or more selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane
  • trialkoxysilane [5] is methyltrimethoxysilane, methyltrimethoxysilane.
  • tetraalkoxysilane [6] is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.
  • chlorosilane compound [9-1] examples include, but are not limited to, the following compounds: Chlorodimethylsilane, chlorodiethylsilane. Among these, a preferable compound is chlorodimethylsilane.
  • silanol compound [9-2] examples include, but are not limited to, the following compounds: Dimethylsilanol, diethylsilanol. Among these, a preferred compound is dimethylsilanol.
  • monoalkoxysilane compound [9-3] include, but are not limited to, the following compounds: Dimethylmethoxysilane, dimethylethoxysilane, diethylmethoxysilane, diethylethoxysilane.
  • preferred compounds include dimethylmethoxysilane and dimethylethoxysilane.
  • disiloxane compound [9-4] include, but are not limited to, the following compounds: 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraethyldisiloxane. Among these, 1,1,3,3-tetramethyldisiloxane is a preferred compound.
  • the hydrolysis condensate [I] can be obtained by advancing the reaction at a predetermined temperature for a predetermined time while stirring the reaction solution.
  • the reaction vessel is preferably equipped with a reflux device. .
  • the amount of dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5] used is not particularly limited.
  • the dialkoxysilane [3]: trialkoxysilane [4] is preferably blended at a molar ratio of 85:15 to 15:85, and 85:15 to 30:70. It is particularly preferable to blend with.
  • the amount is 1 to 80 mol with respect to 100 mol in total of dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5]. It is preferably 1 to 60 mol, particularly preferably.
  • the amount of water used is not particularly limited.
  • the total molar equivalent of alkoxy groups contained in the alkoxysilane compound of the raw material compound that is, alkoxy contained in dialkoxysilane [3], trialkoxysilane [4] and tetraalkoxysilane [5] It is preferably 1.5 times or more and 5 times or less with respect to the total molar equivalent of the group.
  • the molar equivalent is 1.5 times or more, the alkoxysilane compound is efficiently hydrolyzed, and it is not necessary to add more than 5 molar equivalents.
  • the reaction can be carried out even under solvent-free conditions, but a reaction solvent can also be used.
  • the type of the reaction solvent is not particularly limited as long as it does not inhibit the reaction for producing the hydrolyzed polycondensate [I].
  • hydrophilic organic solvents such as alcohols are preferable.
  • Specific examples of the alcohols include methanol, ethanol, normal propanol, isopropanol, and butanol, but are not limited thereto.
  • the amount of the reaction solvent used is preferably 0.1 to 1000% by mass, particularly preferably 1 to 300% by mass, based on the total amount of the alkoxysilane compound used.
  • alcohols generated from the alkoxysilane compound as a reaction raw material in the reaction process function as a reaction solvent, it may not always be necessary to add.
  • an acidic catalyst or a basic catalyst can be used as the type of catalyst used in the production of the hydrolyzed polycondensate [I].
  • Use of an acidic catalyst is preferred because the molecular weight of the hydrolyzed polycondensate [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 of the catalyst used in the production of the hydrolyzed polycondensate [I] is preferably 0.001 to 5% by mass, particularly preferably 0.005 to 1%, based on the total amount of the alkoxysilane compound, solvent and water used. % By mass.
  • reaction time in the production of the hydrolyzed polycondensate [I] is not particularly limited, and may be 3 hours or more and 15 hours or less.
  • Reaction temperature is not specifically limited, 60 degreeC or more and 120 degrees C or less may be sufficient, and 80 degreeC or more and 100 degrees C or less are preferable.
  • This separation method is not particularly limited.
  • the separation method include an extraction method. Specifically, after the temperature of the reaction solution after the above reaction is lowered to room temperature, the hydrolyzed polycondensate [I] present in the reaction system is extracted by contacting with a non-aqueous organic solvent as an extraction solvent. Next, the catalyst contained in the solution after extraction is removed.
  • the method for removing the catalyst is not particularly limited. For example, if the catalyst (for example, acetic acid) used is water-soluble, this catalyst can be removed by washing the solution after extraction with water.
  • a desiccant is added to the solution after removing the catalyst to remove water dissolved in the system. Furthermore, high purity hydrolysis polycondensate [I] can be separated by removing the desiccant and removing the extraction solvent under reduced pressure. At this time, water may be simultaneously removed under reduced pressure in the process of removing the extraction solvent from the solution after removing the catalyst under reduced pressure without using a desiccant.
  • a non-aqueous organic solvent can be used as the extraction solvent.
  • the kind of this non-aqueous organic solvent is not specifically limited. Examples thereof include aromatic hydrocarbons and ethers. Specific examples include toluene, diethyl ether, isopropyl ether, dibutyl ether, and the like, but are not limited thereto.
  • the desiccant is not particularly limited as long as water can be removed from the system and separated from the hydrolyzed polycondensate [I].
  • a solid desiccant is preferably used. Specifically, although magnesium sulfate etc. are mentioned, it is not limited to this.
  • the separated and purified hydrolyzed polycondensate [I] may be further subjected to a condensation reaction by heating and stirring in a solvent or under heating without solvent. Thereby, the molecular weight of hydrolysis polycondensate [I] can be increased.
  • a solvent used, the hydrolysis polycondensate [I] and the solvent are put into a reaction vessel capable of being heated to reflux to obtain a solution. The solution is heated to reflux and azeotroped with water generated in the system as the condensation proceeds. At this time, tosylic 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 condensate [I] and can be heated to reflux.
  • the hydrolysis polycondensate [I] is charged into a reaction vessel capable of being heated and stirred, heated to 100 ° C. or higher and 150 ° C. or lower and stirred for 6 to 18 hours. At this time, in order to suppress the change in the composition ratio of the hydrolyzed polycondensate [I], it is preferable to provide the reaction vessel with a reflux device (for example, a condenser). After heating and stirring, the content liquid is cooled to room temperature.
  • a reflux device for example, a condenser
  • the first method is to react hydrolysis polycondensate (I) with chlorosilane compound [9-1], which is a kind of silane compound [9], in a water-insoluble organic solvent, and Refers to the method of manufacturing.
  • the second method is a hydrolysis polycondensate (I) and a silanol compound [9-2], a monoalkoxysilane compound [9-3] or a disiloxane compound [9-] which is a kind of silane compound [9]. 4] in the presence of an acid in a mixed solvent of a water-insoluble organic solvent and an alcoholic solvent to produce the component (A).
  • (First method) In the first method, first, a predetermined amount of the hydrolyzed polycondensate (I) and a non-aqueous organic solvent are placed in a reaction vessel to dissolve the hydrolyzed polycondensate (I). Next, a predetermined amount of the chlorosilane compound [9-1] 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. Then, (A) component can be obtained by terminating reaction.
  • the amount of the hydrolyzed polycondensate (I) and the chlorosilane compound [9-1] used is not particularly limited. From the viewpoint of the physical properties of the component (A), it is preferable to use 0.2 to 10 mmol of the chlorosilane compound [9-1] with respect to 1 g of the hydrolyzed polycondensate (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 (A).
  • 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, based on 1 g of the hydrolyzed polycondensate (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
  • the component (A) is separated from the reaction system and purified from the viewpoint of handling the component (A).
  • 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 (A) 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. It is preferable that the component (A) after the separation further removes water contained in the component (A) by heating and stirring without solvent and under reduced pressure.
  • the heating temperature at this time is not particularly limited, but is usually 100 to 130 ° C.
  • a hydrolysis polycondensate (I), a non-aqueous organic solvent, and optionally an alcoholic solvent are put in a predetermined amount in a reaction vessel, and the hydrolysis polycondensate (I) is added. Dissolve. Next, a predetermined amount of silanol compound [9-2], monoalkoxysilane compound [9-3] or disiloxane compound [9-4] is added to the solution. Further, 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 [9-2], monoalkoxysilane compound [9-3] or disiloxane compound [9-4] used is not particularly limited. .
  • silanol compound [9-2], monoalkoxysilane compound [9-3] or disiloxane compound [9-4] per 1 g of hydrolyzed polycondensate (I) The SiH group is preferably used in the range of 0.2 mmol 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 (A) 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 used is preferably 50 to 1000% by mass, particularly preferably 100 to 500% by mass, based on 1 g of the hydrolyzed polycondensate (I).
  • the type of alcohol solvent used is not particularly limited as long as the reaction for producing the component (A) 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 the catalyst to be used is not particularly limited as long as it has an action of promoting the reaction for producing the component (A).
  • 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 0.0001 to 10 mmol%, particularly preferably 0.005 to 5 mmol%, based on 1 g of the hydrolyzed polycondensate (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
  • 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 (A) 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 (A) after the separation further removes water contained in the component (A) by heating and stirring without solvent and under reduced pressure.
  • the heating temperature at this time is not particularly limited, but is usually 100 to 130 ° C.
  • the manufacturing method of (B) component is not specifically limited.
  • hydrolysis polycondensation of a dialkoxysilane compound represented by the following general formula [6], a trialkoxysilane compound represented by the general formula [7] and a tetraalkoxysilane compound represented by the general formula [8] A condensate obtained by the reaction (hereinafter sometimes referred to as “hydrolyzed polycondensate [II]”), and a general formula [10-1], [10-2], [10-3] or [10 -4] can be reacted with a vinylsilane compound represented by
  • the R 5 in the general formula [6] has the same meaning as R 5 in formula [2], R 10 represents an alkyl group having 1-3 carbon atoms, two R 10 may be the same or different types from each other Good.
  • R 6 in the general formula [7] has the same meaning as R 6 in the formula [2]
  • R 11 represents an alkyl group having 1 to 3 carbon atoms
  • three R 11 may be the same or different types from each other Good
  • R 12 in the general formula [8] represents an alkyl group having 1 to 3 carbon atoms
  • the four R 12 may be the same or different from each other.
  • Formula [10-1], [10-2], R 4 in the [10-3] and [10-4] has the same meaning as R 4 in the formula [2].
  • R 14 in the general formula [10-3] represents an alkyl group having 1 to 3 carbon atoms.
  • dialkoxysilane compound represented by the general formula [6] the trialkoxysilane compound represented by the general formula [7]
  • the tetraalkoxysilane compound represented by the general formula [8] are referred to as “dialkoxysilane”, respectively.
  • [6] “trialkoxysilane [7]”, “tetraalkoxysilane [8]”.
  • the vinylsilane compounds represented by the general formulas [10-1], [10-2], [10-3] and [10-4] are “chlorovinylsilane compound [10-1]” and “vinylsilanol”, respectively.
  • Compound [10-2] “monoalkoxyvinylsilane compound [10-3]”
  • Compound [10] ".
  • dialkoxysilane [6] include, but are not limited to, the following compounds: Dimethyldimethoxysilane, dimethyldiethoxysilane, ethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane.
  • preferred compounds include dimethyldimethoxysilane and dimethyldiethoxysilane.
  • trialkoxysilane [7] include, but are not limited to, the following compounds: Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxy Silane, 3- (trifluoromethyl) phenyltriethoxysilane, 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane, 3,5- (ditrifluoromethyl) phenyltrimethoxy Silane, 3,5- (ditrifluoromethyl) phenyltriethoxysilane, naphthyltrimethoxysilane, naphthyltri
  • preferred compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3- (trifluoromethyl) phenyltrimethoxysilane, and 3- (trifluoromethyl) phenyltriethoxysilane.
  • 4- (trifluoromethyl) phenyltrimethoxysilane, 4- (trifluoromethyl) phenyltriethoxysilane 3,5- (ditrifluoromethyl) phenyltrimethoxysilane, 3,5- (ditrifluoromethyl) phenyltriethoxy Silanes can be mentioned, and particularly preferable compounds include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.
  • tetraalkoxysilane [8] include, but are not limited to, the following compounds: Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane.
  • preferred compounds include tetramethoxysilane and tetraethoxysilane.
  • dialkoxysilane [6], trialkoxysilane [7] and tetraalkoxysilane [8] used for the production of component (B) is not particularly limited.
  • the dialkoxysilane [6], trialkoxysilane [7] and tetraalkoxysilane [8] may be used alone or in combination.
  • dialkoxysilane [6] is selected from the group consisting of dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and diethyldiethoxysilane, and trialkoxysilane [7] is methyltrimethoxysilane [7].
  • dialkoxysilane [6] is one or more selected from the group consisting of dimethyldimethoxysilane and dimethyldiethoxysilane
  • trialkoxysilane [7] is methyltrimethoxysilane, methyltrimethoxysilane.
  • tetraalkoxysilane [8] is selected from the group consisting of tetramethoxysilane and tetraethoxysilane.
  • chlorovinylsilane compound [10-1] include, but are not limited to, the following compounds: Chlorodimethylvinylsilane, chlorodiethylvinylsilane. Among these, a preferred compound is chlorodimethylvinylsilane.
  • vinylsilanol compound [10-2] include, but are not limited to, the following compounds: Dimethyl vinyl silanol, diethyl vinyl silanol. Among these, a preferable compound is dimethylvinylsilanol.
  • monoalkoxyvinylsilane compound [10-3] include, but are not limited to, the following compounds: Dimethylmethoxyvinylsilane, dimethylethoxyvinylsilane, diethylmethoxyvinylsilane, diethylethoxyvinylsilane.
  • preferred compounds include dimethylmethoxyvinylsilane and dimethylethoxyvinylsilane.
  • divinyldisiloxane compound [10-4] include, but are not limited to, the following compounds: 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraethyl-1,3-divinyldisiloxane. Among these, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane is a preferred compound.
  • the hydrolyzed polycondensate [II] can be produced by applying the above-described method for producing the hydrolyzed polycondensate [I]. That is, dialkoxylane [3], trialkoxysilane [4], and tetraalkoxysilane [5] in the method for producing the hydrolysis polycondensate [I] described above are dialkoxysilane [6] and trialkoxysilane [7], respectively. ], Tetraalkoxysilane [8] is substituted, and hydrolyzed polycondensate [I] is replaced with hydrolyzed polycondensate [II], whereby the method for producing hydrolyzed polycondensate [II] can be explained. .
  • the component (B) can be produced by applying the method for producing the component (A) from the hydrolysis polycondensate [I] described above.
  • Compound [9-4] is vinylsilane compound [10], chlorovinylsilane compound [10-1], vinylsilanol compound [10-2], monoalkoxyvinylsilane compound [10-3], divinyldisiloxane compound [10-4], respectively.
  • the SiH group, the hydrolysis polycondensate [I], and the component (A) are replaced with the Si—CH ⁇ CH 2 group, the hydrolysis polycondensate [II], and the component (B), respectively.
  • a method for producing the component (B) from the polycondensate [II] can be described.
  • component (C) As the component (C), a commercially available product may be used, or a synthesized product may be used.
  • the component (C) can be synthesized by a conventionally known method.
  • the cured product of the present invention can be obtained by heating 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 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 curing the composition of the present invention is not particularly limited.
  • the composition of the present invention is sealed like an LED by a method such as injection, dripping, casting, casting, extrusion from a container, or by integral molding by transfer molding or injection molding.
  • the composition can be cured to form a cured product, and the object to be sealed can be sealed. If the heating temperature is 45 ° C. or higher, stickiness is hardly observed in the obtained cured product, and if it is 300 ° C. or lower, foaming is hardly observed in the obtained cured product, which is practical.
  • 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 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.
  • a nuclear magnetic resonance apparatus manufactured by JEOL Ltd., model number: ECA-400 having a resonance frequency of 400 MHz was used.
  • the chemical shift of each functional group in the silicone resin is shown below: Me: 0.0 to 0.5 ppm
  • a peak (i) area / total peak area sum
  • b peak (a) area + peak (b) area) / total peak area
  • c peak (c) area + peak (d) area + peak (e) area) / total peak area
  • d peak (f) area + peak (g) area + peak (h) area) / total peak area.
  • e sum of peak (j) area / total peak area
  • f peak (a) area + peak (b) area) / total peak area
  • g peak (c) area + peak (d) area + peak (e) area) / total peak area
  • h peak (f) area + peak (g) area + peak (h) area) / total peak area.
  • the ratio of 29 Si-NMR of peak (i) and peak (j) was calculated from the integral ratio of 1 H-NMR, and the overlap of peak (a) with peak (i) and peak (j)
  • the integration value of peak (a) was calculated by subtracting the integration ratio of peak (i) and peak (j) calculated from the integrated value. In other cases, when 29 Si-NMR peaks overlapped, the calculation was performed based on the integration ratio of 1 H-NMR in the same manner as described above.
  • Mass average molecular weight (Mw) measurement The mass average molecular weight (Mw) of the silicone resin was calculated by creating a calibration curve using polystyrene as a reference material by the gel permeation chromatography (abbreviation: GPC) method under the following conditions: Device: manufactured by Tosoh Corporation, product name: HLC-8320GPC, Column: manufactured by Tosoh Corporation, product name: TSK gel Super HZ 2000x4, 3000x2, Eluent: tetrahydrofuran.
  • GPC gel permeation chromatography
  • a calibration curve was prepared using polystyrene as a reference substance by a gel permeation chromatography (abbreviation: GPC) method under the following conditions, and values were calculated: Device: manufactured by Tosoh Corporation, product name: HLC-8320GPC, Column: manufactured by Tosoh Corporation, product name: TSK gel Super HZM-Hx2 Eluent: tetrahydrofuran.
  • GPC gel permeation chromatography
  • the refractive index of the silicone resin was measured using a refractometer (Kyoto Electronics Industry Co., Ltd., model: RA-600).
  • Viscosity measurement Regarding the viscosity of the silicone resin, a rotational viscometer (Brookfield Engineering Laboratories, Inc., product name: DV-II + PRO) and a temperature control unit (Brookfield Engineering Laboratories, Inc., product name: THERMOSEL) are used, 25 The value at ° C was measured.
  • the 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 collected, and toluene was distilled off under reduced pressure using an evaporator to obtain a silicone resin (I-1) as a colorless viscous liquid.
  • the yield of the silicone resin (I-1) is 160.8 g, the mass average molecular weight (Mw) is 1,000, and the composition ratio is (Me 2 SiO 2/2 ) 0.43 (PhSiO 3/2 ) 0.57 .
  • the HO—Si group content was 7.8 mmol / g (13 mass%).
  • silicone resin (A1) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (A1) is 42.5 g
  • the mass average molecular weight (Mw) is 1,900
  • the viscosity is 200 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.31 (PhSiO 3/2 ) 0.42 (H (Me) 2 SiO 1/2 ) 0.27
  • the H—Si group content is 2.8 mmol / g
  • the HO—Si group content is 2.0 mmol / g (3.4 mass%).
  • silicone resin (B1) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (B1) is 20.6 g
  • the mass average molecular weight (Mw) is 1,800
  • the viscosity is 350 cP
  • the content of HO-Si group is 2.1 mmol / g (3 .6 mass%).
  • the yield of the silicone resin (I-2) is 163.0 g, the mass average molecular weight (Mw) is 900, and the composition ratio of the product is (Me 2 SiO 2/2 ) 0.41 (PhSiO 3/2 ) 0.52 ( SiO 4/2 ) 0.06 , and the HO—Si group content was 8.5 mmol / g (14% by mass).
  • silicone resin (A2) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (A2) is 55.1 g
  • the mass average molecular weight (Mw) is 1,000
  • the viscosity is 140 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.21 (PhSiO 3/2 0.45 (SiO 4/2 ) 0.06 (H (Me) 2 SiO 1/2 ) 0.28
  • the H—Si group content is 2.6 mmol / g
  • the HO—Si group content is 2. It was 9 mmol / g (4.9 mass%).
  • silicone resin (B2) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (B2) is 29.5 g
  • the weight average molecular weight (Mw) is 1,100
  • the viscosity is 200 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.26 (PhSiO 3/2 ) 0.42 (SiO 4/2 ) 0.05 (CH 2 ⁇ CH (Me) 2 SiO 1/2 ) 0.27
  • CH 2 ⁇ CH—Si group content is 2.7 mmol / g
  • HO— The Si group content was 1.7 mmol / g (2.9% by mass).
  • the yield of the silicone resin (I-3) is 154.2 g, the mass average molecular weight (Mw) is 900, and the composition ratio is (Me 2 SiO 2/2 ) 0.35 (PhSiO 3/2 ) 0.56 (SiO 4 / 2 ) It was 0.10 , and the content of HO—Si groups was 8.5 mmol / g (14% by mass).
  • silicone resin (A3) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (A3) is 58.4 g
  • the mass average molecular weight (Mw) is 1,100
  • the viscosity is 180 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.15 (PhSiO 3/2 0.46 (SiO 4/2 ) 0.07 (H (Me) 2 SiO 1/2 ) 0.33
  • the H—Si group content is 3.2 mmol / g
  • the HO—Si group content is 2. It was 7 mmol / g (4.6% by mass).
  • Toluene was distilled off from the organic layer by an evaporator, followed by vacuum distillation (130 ° C., 2 hours) by heating to obtain a silicone resin (B3) as a colorless and transparent viscous liquid.
  • the yield of the silicone resin (B3) is 32.7 g
  • the weight average molecular weight (Mw) is 1,300
  • the viscosity is 230 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.20 (PhSiO 3/2 0.43 (SiO 4/2 ) 0.07 (CH 2 ⁇ CH (Me) 2 SiO 1/2 ) 0.30
  • CH 2 ⁇ CH—Si group content is 2.8 mmol / g
  • HO—Si group The content of was 1.7 mmol / g (2.9% by mass).
  • the yield of the silicone resin (I-4) is 143.4 g, the mass average molecular weight (Mw) is 1,100, and the composition ratio is (Me 2 SiO 2/2 ) 0.34 (PhSiO 3/2 ) 0.51 (SiO 4/2 ) 0.15 , and the HO—Si group content was 7.7 mmol / g (13 mass%).
  • silicone resin (A4) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (A4) is 165.7 g
  • the mass average molecular weight (Mw) is 1,500
  • the viscosity is 4,000 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.16 (PhSiO 3 / 2 ) 0.45 (SiO 4/2 ) 0.15 (H (Me) 2 SiO 1/2 ) 0.24
  • the H—Si group content is 2.2 mmol / g
  • the HO—Si group content is It was 3.1 mmol / g (5.3 mass%).
  • silicone resin (B4) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (B4) is 99.2 g
  • the weight average molecular weight (Mw) is 1,400
  • the viscosity is 2,500 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.23 (PhSiO 3/2 ) 0.41 (SiO 4/2 ) 0.13 (CH 2 ⁇ CH (Me) 2 SiO 1/2 ) 0.23
  • CH 2 ⁇ CH—Si group content is 2.2 mmol / g
  • HO—Si group content is It was 1.9 mmol / g (3.2% by mass).
  • the yield of the silicone resin (I-5) is 137.7 g, the mass average molecular weight (Mw) is 1,300, and the composition ratio is (Me 2 SiO 2/2 ) 0.28 (PhSiO 3/2 ) 0.53 (SiO 4/2 ) 0.19 , and the HO—Si group content was 7.4 mmol / g (13 mass%).
  • silicone resin (A5) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (A5) is 27.5 g
  • the weight average molecular weight (Mw) is 1,600
  • the viscosity is 15,000 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.13 (PhSiO 3 / 2 ) 0.43 (SiO 4/2 ) 0.21 (H (Me) 2 SiO 1/2 ) 0.23
  • the H—Si group content is 2.1 mmol / g
  • the HO—Si group content is It was 2.7 mmol / g (4.6% by mass).
  • silicone resin (B5) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (B5) is 15.2 g
  • the mass average molecular weight (Mw) is 1,500
  • the viscosity is 23,000 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.18 (PhSiO 3 / 2 ) 0.40 (SiO 4/2 ) 0.19 (CH 2 ⁇ CH (Me) 2 SiO 1/2 ) 0.23
  • CH 2 ⁇ CH—Si group content is 2.3 mmol / g
  • Si— The OH group content was 1.7 mmol / g (2.9% by mass).
  • the yield of the silicone resin (I-6) is 140.8 g, the weight average molecular weight (Mw) is 1,500, and the composition ratio is (Me 2 SiO 2/2 ) 0.29 (PhSiO 3/2 ) 0.44. (SiO 4/2 ) 0.27 , and the HO—Si group content was 6.8 mmol / g (12 mass%).
  • silicone resin (A6) As a colorless and transparent viscous liquid.
  • the yield of the silicone resin (A6) is 59.3 g
  • the weight average molecular weight (Mw) is 1,900
  • the viscosity is 280,000 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.15 (PhSiO 3 / 2 ) 0.40 (SiO 4/2 ) 0.22 (H (Me) 2 SiO 1/2 ) 0.23
  • the H—Si group content is 1.6 mmol / g
  • the HO—Si group content is It was 2.5 mmol / g (4.3 mass%).
  • Toluene was distilled off from the organic layer by an evaporator, followed by vacuum distillation (130 ° C., 2 hours) by heating to obtain a silicone resin (B6) as a colorless and transparent viscous liquid.
  • the yield of the silicone resin (B6) is 32.0 g
  • the mass average molecular weight (Mw) is 1,900
  • the viscosity is 280,000 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.19 (PhSiO 3 / 2 ) 0.39 (SiO 4/2 ) 0.21 (CH 2 ⁇ CH (Me) 2 SiO 1/2 ) 0.21
  • the CH 2 ⁇ CH—Si group content is 1.9 mmol / g
  • HO— The Si group content was 1.6 mmol / g (2.7% by mass).
  • the yield of the silicone resin (DA1) is 144.2 g
  • the mass average molecular weight (Mw) is 1,400
  • the viscosity is 34,000 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.34 ( PhSiO 3/2 ) 0.42 (HSiO 3/2 ) 0.24
  • the H—Si group content is 1.5 mmol / g
  • the HO—Si group content is 7.2 mmol / g (12% by mass).
  • reaction solution was returned to room temperature, transferred to a 1 L separatory funnel, 200 mL of toluene and 200 mL of water were added, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed twice with 200 mL of water. Thereafter, the organic layer was collected, and toluene was distilled off under reduced pressure using an evaporator to obtain a silicone resin (DA2) as a colorless viscous liquid.
  • DA2 silicone resin
  • the yield of the silicone resin (DA2) is 81.6 g, the mass average molecular weight (Mw) is 650, the viscosity is 300 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.38 (PhSiO 3/2 ) 0.40. (H (Me) 2 SiO 1/2 ) 0.22 , the H—Si group content is 1.55 mmol / g, and the HO—Si group content is 4.7 mmol / g (8.0% by mass). )Met.
  • reaction solution was returned to room temperature, transferred to a 1 L separatory funnel, 100 mL of toluene and 100 mL of water were added, and after performing a liquid separation operation, the aqueous layer was removed. Next, the organic layer was washed twice with 100 mL of water. Thereafter, the organic layer was collected, and toluene was distilled off under reduced pressure using an evaporator to obtain a silicone resin (DB2) as a colorless viscous liquid.
  • DB2 silicone resin
  • a silicone resin (DB3) was obtained as a colorless viscous liquid.
  • the yield of the silicone resin (DB3) is 89.3 g
  • the mass average molecular weight (Mw) is 630
  • the viscosity is 300 cP
  • HO-Si group content is 6.8 mmol / g. (12% by mass).
  • composition ratios and physical property values in the synthesized silicone resins (A1) to (A6), silicone resins (B1) to (B6), and silicone resins (DA1) to (DA2), (DB1) to (DB3)
  • Table 2 shows the group content, SiH group or Si—CH ⁇ CH 2 group content, mass average molecular weight, viscosity, refractive index, and transparency.
  • Vi represents a vinyl group (CH 2 ⁇ CH— group).
  • the starting temperature and the appearance upon curing were measured as follows.
  • the composition used for the measurement was composed of (A) component silicone resin [silicone resins (A1) to (A6), (DA1) to (DA2)] and (B) component silicone resin [silicone resin (B1).
  • (DB1) to (DB3)] are blended at a mass ratio of 2: 1 and mixed with the platinum catalyst of component (C) to prepare the compositions of Examples 1 to 6 and Comparative Examples 1 to 3.
  • the platinum catalyst a platinum-divinyltetramethyldisiloxane complex was used so that the content of platinum atoms was 0.03 ppm in mass units with respect to the total amount of the composition.
  • Viscosity of composition Regarding the viscosity of the prepared composition, a rotational viscometer (Brookfield Engineering Laboratories, Inc., product name: DV-II + PRO) and a temperature control unit (Brookfield Engineering Laboratories, Inc., product name: THERMOSEL) were used. The value at 25 ° C. was measured at a shear rate of 30 [1 / s].
  • the prepared composition was poured into a mold (25 mm ⁇ ), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a cured product having a thickness of 4 to 5 mm.
  • the hardness of Shore A or Shore D of this cured product is determined according to JIS K 7215 “Durometer Hardness Test Method for Plastics” using a durometer (manufactured by TECLOCK, model: GS-719R, GS-720R). It was measured by. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.
  • Linear thermal expansion coefficient of cured product 0.7 g of the prepared composition is added to a fluororesin tube (inner diameter: 5.8 mm ⁇ , height: 1.8 mm), heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to obtain a cured product.
  • the linear thermal expansion coefficient of the cured product was measured by heating the cured product from 25 ° C. to 200 ° C. at a temperature increase rate of 5 ° C./min in the air using ThermoPlusTMA8310 (manufactured by Rigaku Corporation). This measurement was performed twice, and the second measured value was adopted. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.
  • the prepared composition was heated in air at 90 ° C. for 1 hour, and further heated at 150 ° C. for 4 hours to produce a cured product.
  • the cured product was measured using a ThermoPlus TG8120 (manufactured by Rigaku Corporation) as a thermogravimetric / differential thermal measurement apparatus (Thermogravimetric / Differential Thermal Analysis, abbreviated as TG-DTA) at a temperature rising rate of 5 ° C./min. It heated from 25 degreeC to 500 degreeC, and measured the temperature ( Td5 ) when a 5% weight loss was carried out. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.
  • a mixture of the prepared composition and zirconia balls having a diameter of 50 ⁇ m is mixed with a glass chip (5.0 mm ⁇ 5.0 mm ⁇ 1.1 mm) and a glass substrate (50 mm ⁇ 50 mm ⁇ 3.0 mm) or an alumina substrate ( 50 mm ⁇ 50 mm ⁇ 2.0 mm), and heated in air at 90 ° C. for 1 hour and further heated at 150 ° C. for 4 hours to be cured.
  • the adhesive strength (adhesive strength) of the prepared sample was measured with a bond tester (manufactured by Daisy Japan Co., Ltd., model: Dage4000Plus). A cured product that was destroyed at the time of measurement and an adhesive strength value could not be obtained was designated as “cohesive failure”. In Comparative Examples 2 and 3, the measurement was not performed because the composition did not cure.
  • Table 3 shows the evaluation results of the compositions and cured products of Examples 1 to 6 and Comparative Examples 1 to 3.
  • the cured products of Examples 1 to 6 showed high transparency of 88% or more at a wavelength of 365 nm and 90% or more at a wavelength of 405 nm.
  • the cured product of Comparative Example 1 had a transmittance of 45% or less. This cause is thought to be due to foaming of the cured product.
  • the transparency (heat-resistant transparency) after the cured product was continuously heated at 200 ° C. for 100 hours the cured products of Examples 1 to 6 were as high as 88% or more at a wavelength of 405 nm and 79% or more at a wavelength of 365 nm. The transmittance was maintained.
  • the cured products of Examples 1 to 6 exhibited T d5 of 285 ° C. or higher, and in particular, the cured products of Examples 3 to 6 exhibited high T d5 of 395 ° C. or higher.
  • the cured products of Examples 1 to 6 show less than 300 ppm by volume, in particular, the cured products of Examples 1 and 3 to 6 show less than 250 ppm by volume, and the cured products of Examples 4 to 6 Shows a good linear thermal expansion coefficient of less than 215 ppm by volume.
  • a low linear thermal expansion coefficient indicates that the volume expansion and shrinkage in the heat cycle is small and the mold is difficult to peel off, so that the linear thermal expansion coefficient is preferably low.
  • the curing start temperature of the compositions of Examples 1 to 6 is as low as 58 to 79 ° C. and has good curability. On the other hand, in Comparative Examples 1 to 3, curing did not start even when the temperature was raised to 150 ° C.
  • compositions of Examples 1 to 6 within the scope of the present invention have good curability, and the cured product has high heat-resistant transparency. Also, the adhesion was good. In particular, it was shown that the cured products of Examples 3 to 6 were excellent in heat resistance and Shore hardness. In addition, the cured products of Examples 4 to 6 were shown to have high adhesive strength.
  • the silicone resin (A1) as the component (A) and the silicone resin (B1) as the component (B) are blended at a mass ratio of 2: 1 and mixed with the platinum catalyst as the component (C).
  • 1-1 to Composition 1-5 were prepared.
  • a comparative composition 1-1 was prepared, in which the platinum catalyst of the component (C) was not blended, and the silicone resin (A1) and the silicone resin (B1) were blended at a mass ratio of 2: 1.
  • the platinum catalyst a platinum-divinyltetramethyldisiloxane complex was used so that the content of platinum atoms was a predetermined amount in mass units with respect to the total amount of the curable silicone resin composition.
  • compositions 4-1 to 4-3 and A comparative composition 4-1 was prepared.
  • the physical properties (transparency and heat-resistant transparency) of the cured product, the curing start temperature, and the appearance of the cured product were determined using the above-mentioned [Transparency of cured product], [Curing Evaluation was performed according to the methods described in "Heat Transparency of Products", “Curing Start Temperature”, and "Appearance upon Curing”. These results are shown in Table 4, FIG. 2 and FIG.
  • the curing start temperature increased as the platinum atom content decreased.
  • the curing start temperature of Composition 1-5 was higher than 150 ° C., but a cured product was obtained without any problem under the curing conditions (heating at 90 ° C. for 1 hour and further heating at 150 ° C. for 4 hours).
  • the transmittance of all the cured products was in the range of 88 to 91% at a wavelength of 405 nm and in the range of 89 to 91% at a wavelength of 365 nm, indicating high transparency.
  • all cured products maintained high transmittance of 85% or more at a wavelength of 405 nm, but at a wavelength of 365 nm.
  • the transmittance of the cured product of Comparative Composition 4-1 was 70%, and a decrease in transparency was observed.
  • the cured products of Composition 1-1 to Composition 1-5 and Composition 4-1 to Composition 4-4 maintained a transparency of 75% or more.
  • Composition 1-1 to Composition 1-5 and Composition 4-1 to Composition 4-4 within the scope of the present invention have good curability and high heat transparency. It was shown that.
  • compositions 1-6 to 1-9 were prepared by blending the agents.
  • the platinum catalyst a platinum-divinyltetramethyldisiloxane complex was used so that the platinum atom content was 2.0 ppm in terms of mass unit with respect to the total mass of the components (A) to (C).
  • the curing retarder was added in the range of 70 to 80 equivalents with a platinum atom content of 2.0 mass ppm as one equivalent.
  • composition 1-6 118 ⁇ g of dimethyl maleate was added as a curing retarder to 1 g of the total composition, and in the preparation of composition 1-7, 3-butyn-2-ol was added.
  • composition 1-8 67 ⁇ g of 2-methyl was added to 1 g of the total amount of the composition, and 94 ⁇ g of 1-ethynyl-1-cyclohexanol was added to 1 g of the total amount of the composition.
  • 86 ⁇ g of tetramethylethylenediamine was added to 1 g of the total amount of the composition.
  • compositions 1-6 to 1-9 and composition 1-1 as an example of a composition not containing a curing retarder, physical properties of these cured products (transparency and heat-resistant transparency)
  • the appearance of the cured product and the curing start time are evaluated according to the methods described in [Transparency of cured product], [Heat-resistant transparency of cured product], [Appearance at curing], and [Curing start time] below. did. These results are shown in Table 5 and FIG.
  • the curing start time was 26 minutes after the composition 1-1, but more than 2 hours after the composition 1-6 to the composition 1-9 to which the curing retarder was added. It was found that the curability can be controlled by adding. Further, the transmittance of the cured products of the compositions 1-6 to 1-9 is 89% or more at a wavelength of 405 nm and 87% or more at a wavelength of 365 nm, and transparency is not impaired by a curing retarder. It was. Furthermore, the transparency (heat-resistant transparency) after the cured product was continuously heated at 200 ° C.
  • the silicone resin (A4) as the component (A) and the silicone resin (B4) as the component (B) are blended at a mass ratio of 2: 1, and the platinum catalyst as the component (C) is mixed.
  • Compositions 4-4 to 4-6 were prepared by blending an agent or an antioxidant.
  • the platinum catalyst a platinum-divinyltetramethyldisiloxane complex was used so that the content of platinum atoms was 0.2 ppm in mass units with respect to the total mass of the components (A) to (C). .
  • the light stabilizer and the antioxidant were added in the range of 0.05 to 0.2% by mass with respect to the total mass of the components (A) to (C).
  • composition 4-4 0.5 mg of bis (2,2,6,6-tetramethyl 4-piperidyl) sebacate as a light stabilizer was added to 1 g of the total composition. .
  • 1.0 mg of bis (2,2,6,6-tetramethyl 4-piperidyl) sebacate as a light stabilizer was added to 1 g of the whole composition.
  • compositions 4-4 to 4-6 and composition 4-1 as an example of a composition not containing a light stabilizer and an antioxidant, the physical properties (transparency and Heat-resistant transparency) and the appearance of the cured product were evaluated according to the methods described in [Appearance at curing] and [Heat-resistant transparency of cured product containing antioxidant] described below.
  • Table 6 shows the evaluation results of the cured products of Composition 4-1 and Composition 4-4 to Composition 4-6.
  • the transmittance after 100 hours and 200 hours after further heating at 200 ° C. is the transmittance after 0 hours (the transmittance in the 405 nm and 365 nm wavelength regions of the cured product before further curing).
  • the composition 4-4 to 4-6 to which a light stabilizer or an antioxidant was added had a smaller transmittance fluctuation ratio than the composition 4-1.
  • the transmittance fluctuation ratio was particularly small. From these results, it was shown that the addition of the light stabilizer or the antioxidant contributes to the improvement of the heat-resistant transparency of the cured product.
  • the mass average molecular weight (Mw) of the silicone resin (II) is 5,200, the composition ratio is (Me 2 SiO 2/2 ) 0.50 (PhSiO 3/2 ) 0.50 , and the content of HO—Si group is 4 0.5 mmol / g (6.7% by mass), and the toluene content was 20.49% by mass.
  • the yield of the silicone resin (A7) is 103.23 g, the mass average molecular weight (Mw) is 6,100, the viscosity is 5,100 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.39 (PhSiO 3 / 2 ) 0.47 (H (Me) 2 SiO 1/2 ) 0.14 , the H—Si group content is 1.26 mmol / g, and the HO—Si group content is 2.66 mmol / g (4 0.5% by mass).
  • the yield of the silicone resin (A8) is 107.48 g, the mass average molecular weight (Mw) is 5,600, the viscosity is 2,800 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.40 (PhSiO 3 / 2 ) 0.48 (H (Me) 2 SiO 1/2 ) 0.12 , the H—Si group content is 1.40 mmol / g, and the HO—Si group content is 2.1 mmol / g (3 .6 mass%).
  • a silicone resin (B8) was obtained.
  • the yield of the silicone resin (B8) is 51.78 g
  • the mass average molecular weight (Mw) is 5,300
  • the viscosity is 5,000 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.39 (PhSiO 3/2 ) 0.44.
  • CH 2 ⁇ CH (Me) 2 SiO 1/2 CH 2 ⁇ CH—Si group content 0.17
  • CH 2 ⁇ CH—Si group content is 1.05 mmol / g
  • HO—Si group content is 2.3 mmol / g. (4.0% by mass).
  • the yield of the silicone resin (A9) is 106.52 g, the mass average molecular weight (Mw) is 5,800, the viscosity is 2,100 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.38 (PhSiO 3 / 2) 0.42 (H (Me ) 2 SiO 1/2) 0.20, the content of H-Si group is 1.81 mmol / g, content of HO-Si groups 1.7 mmol / g (2 0.9 mass%).
  • the yield of the silicone resin (A10) is 110.66 g, the mass average molecular weight (Mw) is 5,700, the viscosity is 1,600 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.35 (PhSiO 3 / 2 ) 0.41 (H (Me) 2 SiO 1/2 ) 0.24 , the H—Si group content is 2.25 mmol / g, and the HO—Si group content is 1.18 mmol / g (2 0.0 mass%).
  • the yield of the silicone resin (A11) is 113.15 g, the mass average molecular weight (Mw) is 5,700, the viscosity is 1,000 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.36 (PhSiO 3 / 2 ) 0.38 (H (Me) 2 SiO 1/2 ) 0.26 , the H—Si group content is 2.7 mmol / g, and the HO—Si group content is 0.86 mmol / g (1 0.5% by mass).
  • the yield of the silicone resin (B11) is 53.64 g, the mass average molecular weight (Mw) is 5,200, the viscosity is 2,500 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.38 (PhSiO 3 / 2 ) 0.45 (CH 2 ⁇ CH (Me) 2 SiO 1/2 ) 0.17 , CH 2 ⁇ CH—Si group content is 1.6 mmol / g, and HO—Si group content is 1 It was 0.8 mmol / g (3.0 mass%).
  • the yield of the silicone resin (A12) is 42.5 g, the weight average molecular weight (Mw) is 1,900, the viscosity is 200 cP, and the composition ratio is (Me 2 SiO 2/2 ) 0.31 (PhSiO 3/2 ) 0.42 (H (Me) 2 SiO 1/2 ) 0.27 , the H—Si group content is 2.8 mmol / g, and the HO—Si group content is 2.0 mmol / g (3.4). Mass%).
  • a silicone resin (B12) was obtained.
  • the yield of the silicone resin (B12) is 20.6 g
  • the mass average molecular weight (Mw) is 1,800
  • the viscosity is 350 cP
  • the composition ratio is (Me 2 SiO 2/2 ) 0.32 (PhSiO 3/2 ) 0.45.
  • CH 2 CH (Me) 2 SiO 1/2
  • CH 2 CH-Si group content is 2.3 mmol / g
  • HO-Si group content is 2.1 mmol / g. (3.6% by mass).
  • composition ratios and physical properties of the synthesized silicone resins (A7) to (A12) and silicone resins (B7) to (B12) are shown in Table 7.
  • Vi represents a vinyl group (CH 2 ⁇ CH— group).
  • ⁇ Curable silicone resin composition and cured product thereof> The viscosity of the prepared composition, the physical properties of the cured product obtained from the composition (hardness, adhesion, transparency, linear thermal expansion coefficient, 5% weight loss temperature, adhesive strength), and appearance upon curing are as described above.
  • the measurement was performed according to the measurement methods of Examples 1 to 6 and Comparative Examples 1 to 3.
  • cured material it measured also about the case where a 6050 SMD type PPA resin package is used instead of a 3528 SMD type PPA resin package, and the measuring method is shown below.
  • the punching moldability of the cured product is shown in the measurement method below.
  • composition used for the measurement was (A) component silicone resin [silicone resins (A7) to (A12)] and (B) component silicone resins [silicone resins (B7) to (B12)].
  • the compositions of Examples 7 to 12 were prepared by blending at a mass ratio of 1 and mixing with the platinum catalyst of component (C).
  • the platinum catalyst a platinum-divinyltetramethyldisiloxane complex was used so that the content of platinum atoms was 0.03 ppm in mass units with respect to the total amount of the composition.
  • Table 8 shows the evaluation results of the compositions and cured products of Examples 7 to 12.
  • the cured products produced in Examples 7 to 12 all have excellent heat-resistant transparency.
  • all cured products showed excellent adhesion to the 3528 SMD type PPA resin package substrate.
  • the cured products of Examples 7 to 9 having a high mass average molecular weight and a high Si—OH group content are larger than the 3528 SMD type PPA resin package.
  • Excellent adhesion to a certain 6050 SMD type PPA resin package was exhibited.
  • the punchability test the cured product of Example 12 having a low mass average molecular weight could not be pulled out because of insufficient resin strength, whereas Examples 7 to 7 having a high mass average molecular weight were used. With the cured product of 11, the cured product could be punched without problems.

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Abstract

L'invention concerne une composition de résine de silicone durcissable caractérisée en ce qu'elle comprend un constituant (A), qui est une résine de silicone contenant des atomes d'hydrogène, chacun lié à un atome de silicium (groupes SiH), un constituant (B), qui est une résine de silicone contenant des groupes vinyle, chacun lié à un atome de silicium (groupes Si-CH=CH2), et un constituant (C), qui est un catalyseur au platine. La composition est en outre caractérisée en ce que la teneur totale de groupes silanol (groupes Si-OH) dans les constituants (A) et (B) est de 0,5 à 5,0 mmoles/g et la teneur d'atomes de platine dans le constituant (C) est de 0,003 à 3,0 ppm en masse de la somme des constituants (A), (B) et (C). Un objet durci obtenu en chauffant la composition convient à une utilisation en tant que matériau d'encapsulation d'un dispositif optique semi-conducteur.
PCT/JP2015/069877 2014-07-24 2015-07-10 Composition de résine de silicone durcissable, objet durci obtenu à partir de celle-ci, et dispositif optique semi-conducteur formé au moyen de celui-ci Ceased WO2016013421A1 (fr)

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CN201580041251.7A CN106574118A (zh) 2014-07-24 2015-07-10 固化性有机硅树脂组合物和其固化物，以及使用它们的光半导体装置
KR1020177003741A KR20170032362A (ko) 2014-07-24 2015-07-10 경화성 실리콘 수지 조성물 및 그 경화물, 및 이들을 이용한 광반도체 장치
US15/328,067 US20170218128A1 (en) 2014-07-24 2015-07-10 Curable Silicone Resin Composition, Cured Object Obtained Therefrom, and Optical Semiconductor Device Formed Using Same

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JP2005325174A (ja) * 2004-05-12 2005-11-24 Asahi Denka Kogyo Kk ケイ素含有硬化性組成物、及びこれを熱硬化させた硬化物
JP2006213789A (ja) * 2005-02-02 2006-08-17 Ge Toshiba Silicones Co Ltd 硬化性オルガノポリシロキサン組成物及び半導体装置
JP2006299099A (ja) * 2005-04-21 2006-11-02 Shin Etsu Chem Co Ltd 光半導体素子封止用樹脂組成物及び光半導体素子
JP2008127517A (ja) * 2006-11-24 2008-06-05 Momentive Performance Materials Japan Kk 半導体封止用シリコーン組成物および半導体装置
JP2009114365A (ja) * 2007-11-08 2009-05-28 Momentive Performance Materials Japan Kk 光半導体用シリコーン接着剤組成物及びそれを用いた光半導体装置
JP2012012524A (ja) * 2010-07-01 2012-01-19 Sekisui Chem Co Ltd 光半導体装置用封止剤及びそれを用いた光半導体装置
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JP2005325174A (ja) * 2004-05-12 2005-11-24 Asahi Denka Kogyo Kk ケイ素含有硬化性組成物、及びこれを熱硬化させた硬化物
JP2006213789A (ja) * 2005-02-02 2006-08-17 Ge Toshiba Silicones Co Ltd 硬化性オルガノポリシロキサン組成物及び半導体装置
JP2006299099A (ja) * 2005-04-21 2006-11-02 Shin Etsu Chem Co Ltd 光半導体素子封止用樹脂組成物及び光半導体素子
JP2008127517A (ja) * 2006-11-24 2008-06-05 Momentive Performance Materials Japan Kk 半導体封止用シリコーン組成物および半導体装置
JP2009114365A (ja) * 2007-11-08 2009-05-28 Momentive Performance Materials Japan Kk 光半導体用シリコーン接着剤組成物及びそれを用いた光半導体装置
JP2012012524A (ja) * 2010-07-01 2012-01-19 Sekisui Chem Co Ltd 光半導体装置用封止剤及びそれを用いた光半導体装置
WO2014115742A1 (fr) * 2013-01-25 2014-07-31 セントラル硝子株式会社 Composition durcissable contenant de la silicone, et article durci associé

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