WO2018173996A1 - Composition de résine durcissable, stratifié et boîtier de semi-conducteur optique - Google Patents

Composition de résine durcissable, stratifié et boîtier de semi-conducteur optique Download PDF

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WO2018173996A1
WO2018173996A1 PCT/JP2018/010739 JP2018010739W WO2018173996A1 WO 2018173996 A1 WO2018173996 A1 WO 2018173996A1 JP 2018010739 W JP2018010739 W JP 2018010739W WO 2018173996 A1 WO2018173996 A1 WO 2018173996A1
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resin composition
group
optical semiconductor
curable resin
organopolysiloxane
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PCT/JP2018/010739
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English (en)
Japanese (ja)
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吉仁 武井
大輔 津島
丈章 齋木
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横浜ゴム株式会社
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Priority to JP2019507655A priority Critical patent/JPWO2018173996A1/ja
Publication of WO2018173996A1 publication Critical patent/WO2018173996A1/fr

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  • the present invention relates to a curable resin composition, a laminate, and an optical semiconductor package.
  • An optical semiconductor package (hereinafter also referred to as an LED) has features such as long life, low power consumption, shock resistance, high-speed response, lightness, thinness, and the like. Development in various fields such as lights, in-vehicle lighting, indoor / outdoor advertising, indoor / outdoor lighting, etc. is making dramatic progress.
  • the LED is usually manufactured by encapsulating an optical semiconductor element by applying a curable resin composition on the optical semiconductor element and curing the composition.
  • a curable resin composition for example, Patent Document 1 discloses a composition containing a plurality of types of organopolysiloxane and a hydrosilylation catalyst.
  • reflectors and electrodes in LEDs are formed with a member (corrosive substrate) containing silver plating or the like, but a sulfur-based gas present in the atmosphere or in the material is used as a sealing material (a curable resin composition).
  • the corrosive substrate may be corroded (sulfurized) through the cured product.
  • sulfurization is a problem because the luminous intensity of the LED decreases.
  • the present inventors prepared a curable resin composition with reference to Patent Document 1 and sealed the optical semiconductor element using this to produce an optical semiconductor package.
  • the present invention provides a curable resin composition, a corrosive substrate, and a curable resin composition that exhibit excellent sulfidation resistance when the optical semiconductor package is used as a sealing material for an optical semiconductor element. It aims at providing the optical semiconductor package obtained by sealing a laminated body provided with the hardened
  • the present inventors have found that the above problems can be solved by blending specific metal particles in the curable silicone resin composition, and have reached the present invention. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • the above (B) (1) to (3), wherein the metal particles to which the organic acid is bound contain at least one metal selected from the group consisting of Ag, Cu, Ni, Co, Au and Pd.
  • the curable resin composition according to any one of the above (1) to (4), wherein the metal particles to which the organic acid (B) is bonded are Ag particles to which the organic acid is bonded.
  • the content of the metal particles to which the (B) organic acid is bonded is 1 to 500 ppm by mass as a metal with respect to 100 parts by mass of the (A) curable silicone resin composition.
  • the (A) curable silicone resin composition is (Aa) an organopolysiloxane having an alkenyl group bonded to a silicon atom; (Ab) an organopolysiloxane having a hydrogen group bonded to a silicon atom;
  • the (A) curable silicone resin composition is (Ad) an organopolysiloxane having a silanol group; (Ae) an organopolysiloxane having an alkoxysilyl group; (Af) The curable resin composition according to any one of the above (1) to (6), comprising a condensation catalyst.
  • the optical semiconductor package when used as an encapsulant for an optical semiconductor element, the optical semiconductor package exhibits excellent sulfidation resistance, a corrosive substrate, and the above curable resin composition.
  • cured material of the thing, and the said curable resin composition can be provided.
  • the optical semiconductor package exhibits excellent sulfidation resistance when used as a sealing material for an optical semiconductor element is also simply referred to as excellent sulfidation resistance.
  • FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
  • FIG. 2 is a cross-sectional view schematically showing another example of the laminate of the present invention.
  • FIG. 3 is a cross-sectional view schematically showing an example of the optical semiconductor package of the present invention.
  • FIG. 4 is a cross-sectional view schematically showing another example of the optical semiconductor package of the present invention.
  • FIG. 5 is a sectional view schematically showing another example of the optical semiconductor package of the present invention.
  • FIG. 6 is a diagram schematically showing an example of an LED display using the composition of the present invention and / or the optical semiconductor package of the present invention.
  • FIG. 7 is a diagram showing the scattering intensity distribution of the dispersion B-1 of specific metal particles.
  • a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the curable resin composition of the present invention contains the following (A) and (B).
  • (B) Metal particles to which organic acid is bound hereinafter also referred to as “specific metal particles”. Since the composition of this invention takes such a structure, it is thought that the effect mentioned above is acquired. The reason for this is not clear, but the metal particles combined with the organic acid contained in the composition of the present invention adsorb sulfur-based gas very efficiently. By using it as a material, the obtained optical semiconductor package is presumed to exhibit excellent sulfidation resistance.
  • the curable silicone resin composition contained in the composition of the present invention is not particularly limited as long as it contains a curable silicone resin.
  • the curable silicone resin composition is preferably in the following first preferred embodiment or the following second preferred embodiment because the effects of the present invention are more excellent.
  • the first preferred embodiment of the curable silicone resin composition is: (Aa) an organopolysiloxane having an alkenyl group bonded to a silicon atom (hereinafter also referred to as “organopolysiloxane (Aa)”); (Ab) an organopolysiloxane having a hydrogen group bonded to a silicon atom (hereinafter also referred to as “organopolysiloxane (Ab)”); (Ac) A curable silicone resin composition containing a hydrosilylation catalyst.
  • organopolysiloxane (AA) is not particularly limited as long as it is an organopolysiloxane having an alkenyl group bonded to a silicon atom.
  • a silicon atom intends a silicon atom of siloxane.
  • alkenyl group examples include alkenyl groups having 2 to 18 carbon atoms such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, and the like. preferable.
  • the alkenyl group in one molecule is preferably 2 to 12% by mass, and more preferably 3 to 10% by mass.
  • AA organopolysiloxane
  • a substituted or unsubstituted monovalent hydrocarbon group monovalent hydrocarbon group
  • a methyl group hereinafter sometimes referred to as “Me”
  • ethyl group ethyl group
  • n-propyl group isopropyl group
  • n-butyl group isobutyl group
  • sec-butyl group sec-butyl group
  • tert-butyl group Alkyl groups having 1 to 18 carbon atoms such as various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, cyclopentyl groups, and cyclohexyl groups
  • aralkyl groups having 7 to 18 carbon atoms such as benzyl groups and phenethyl groups
  • a halogenated alkyl group having 1 to 18 carbon atoms such as a chloropropyl group or a 3
  • alkoxy group examples include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
  • At least 30 mol% of the silicon-bonded total organic groups are preferably aryl groups, and more preferably at least 40 mol% are aryl groups. This reduces attenuation due to light refraction, reflection, scattering, etc. of the resulting cured product, and is excellent in compatibility with the organopolysiloxane (Ab) described later, thereby suppressing turbidity and the like. Excellent in properties.
  • a preferred embodiment of the organopolysiloxane (Aa) includes, for example, an organopolysiloxane represented by the following average unit formula (A).
  • the average unit formula (A) represents the number of moles of each siloxane unit when the total number of siloxane units constituting the organopolysiloxane is 1 mole.
  • R 1 , R 2 and R 3 are each independently a hydrogen group or a substituted or unsubstituted monovalent hydrocarbon group.
  • the monovalent hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various pentyl groups, and various hexyl groups.
  • Alkyl groups having 1 to 18 carbon atoms such as various octyl groups, various decyl groups, cyclopentyl groups, and cyclohexyl groups; vinyl groups (hereinafter sometimes referred to as “Vi”), allyl groups, butenyl groups, pentenyl groups, hexenyls.
  • An alkenyl group having 2 to 18 carbon atoms such as a group or an octenyl group; an aryl group having 6 to 18 carbon atoms such as a phenyl group, a tolyl group or a xylyl group; an aralkyl group having 7 to 18 carbon atoms such as a benzyl group or a phenethyl group; And a halogenated alkyl group having 1 to 18 carbon atoms such as 3-chloropropyl group and 3,3,3-trifluoropropyl group.
  • Two R 2 may be the same or different.
  • Three R 3 may be the same or different.
  • At least one of R 1, R 2 and R 3 (preferably two or more) is an alkenyl group, R 1, R 2 and R 3 and 2 to 12% by weight of an alkenyl group Is preferable, and 3 to 10% by mass is more preferable.
  • at least one of R 1 , R 2 and R 3 is preferably an aryl group, and at least 30 mol% of the total of R 1 , R 2 and R 3 is more preferably an aryl group.
  • at least 40 mol% is an aryl group.
  • X 1 is a hydrogen group or an alkyl group.
  • alkyl group examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, various pentyl groups, various hexyl groups, and various octyl groups.
  • Groups, various decyl groups, cyclopentyl groups, cyclohexyl groups and the like, and alkyl groups having 1 to 18 carbon atoms, and a methyl group is preferable.
  • a is 0 or a positive number
  • b is 0 or a positive number
  • c is 0 or a positive number
  • d is 0 or a positive number
  • e is 0 or a positive number.
  • a + b + c + d + e is 1 or less.
  • b / a is preferably a number in the range of 0 to 10
  • c / a is preferably a number in the range of 0 to 5
  • d / (a + b + c + d) is in the range of 0 to 0.3.
  • e / (a + b + c + d) is preferably a number within the range of 0 to 0.4.
  • the weight average molecular weight (Mw) of the organopolysiloxane (Aa) is preferably 500 to 1,000,000, and more preferably 1,000 to 50,000.
  • a weight average molecular weight shall be the weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) which uses chloroform as a solvent.
  • the content of the organopolysiloxane (Aa) in the composition of the present invention is not particularly limited, but for the reason that the effect of the present invention is more excellent,
  • the content is preferably 10 to 95% by mass, more preferably 50 to 90% by mass, based on the entire composition.
  • organopolysiloxane (Ab) is not particularly limited as long as it is an organopolysiloxane having a hydrogen group bonded to a silicon atom.
  • a silicon atom intends a silicon atom of siloxane.
  • Hydrogen group The hydrogen group is a group represented by —H.
  • a preferred embodiment of the organopolysiloxane (Ab) is, for example, an organopolysiloxane represented by the following average unit formula (B).
  • the average unit formula (B) represents the number of moles of each siloxane unit when the total number of siloxane units constituting the organopolysiloxane is 1 mole.
  • R 1 , R 2 and R 3 are each independently a hydrogen group or a substituted or unsubstituted monovalent hydrocarbon group. Specific examples of the monovalent hydrocarbon group are the same as R 1 , R 2 and R 3 in the above-described formula (A). However, at least one (preferably two or more) of R 1 , R 2 and R 3 in one molecule is a hydrogen group. Further, in one molecule, at least one of R 1 , R 2 and R 3 is preferably an aryl group, and at least 30 mol% of the total of R 1 , R 2 and R 3 is more preferably an aryl group. Preferably, at least 40 mol% is an aryl group.
  • a is 0 or a positive number
  • b is 0 or a positive number
  • c is 0 or a positive number
  • d is 0 or a positive number
  • e is 0 or a positive number.
  • a + b + c + d + e is 1 or less.
  • the preferred embodiments of a, b, c, d and e are the same as a, b, c, d and e in the above formula (A).
  • a preferred embodiment of the molecular weight of the organopolysiloxane (Ab) is the same as that of the above-described organopolysiloxane (Aa).
  • Si—H / Si—Vi molar ratio between the hydrogen group bonded to the silicon atom of the organopolysiloxane (Ab) and the alkenyl group bonded to the silicon atom of the organopolysiloxane (Aa).
  • the molar ratio (hereinafter also referred to as “Si—H / Si—Vi molar ratio” for convenience) is not particularly limited, but is preferably 0.05 to 5.00 because the effect of the present invention is more excellent. 0.10 to 2.00, more preferably 0.50 to 1.50, and particularly preferably 0.70 to 1.10.
  • the hydrosilylation catalyst functions as a catalyst for promoting the addition reaction (hydrosilylation reaction) between the organopolysiloxane (Aa) and the organopolysiloxane (Ab).
  • a conventionally well-known thing can be used as a hydrosilylation catalyst, For example, a platinum-type catalyst, a rhodium-type catalyst, a palladium-type catalyst etc. are mentioned, A platinum-type catalyst is preferable.
  • platinum catalyst examples include chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-divinyltetramethyldisiloxane complex, chloroplatinic acid-alcohol coordination compound, platinum diketone complex, platinum divinyltetramethyldi A siloxane complex etc. are mentioned, These may be used individually by 1 type and may use 2 or more types together.
  • the content of the hydrosilylation catalyst is not particularly limited, but is 0.001 to 100 ppm by mass as a metal (for example, Pt) with respect to the entire composition of the present invention because the curability of the composition of the present invention is excellent. ( ⁇ 10 ⁇ 6 mass%) is preferable.
  • the second preferred embodiment of the curable silicone resin composition is: (Ad) an organopolysiloxane having a silanol group (hereinafter also referred to as “organopolysiloxane (Ad)”); (Ae) an organopolysiloxane having an alkoxysilyl group (hereinafter also referred to as “organopolysiloxane (Ae)”); (Af) A curable silicone resin composition containing a condensation catalyst.
  • organopolysiloxane (Ad) is an organopolysiloxane having one or more, preferably two or more silanol groups in one molecule.
  • silanol group is a hydroxy group bonded to a silicon atom.
  • the content of the organopolysiloxane (Ad) in the composition of the present invention is not particularly limited, but for the reason that the effect of the present invention is more excellent,
  • the content is preferably 10 to 90% by mass, more preferably 50 to 80% by mass, based on the entire composition.
  • organopolysiloxane (Ae) is not particularly limited as long as it is an organopolysiloxane having an alkoxysilyl group.
  • a silicon atom intends a silicon atom of siloxane.
  • Alkoxysilyl group is an alkoxy group (—OR) bonded to a silicon atom.
  • R represents a monovalent hydrocarbon group. Specific examples of the monovalent hydrocarbon group are the same as R 1 , R 2 and R 3 in the above-described formula (A).
  • a preferred embodiment of the molecular weight of the organopolysiloxane (Ae) is the same as that of the above-described organopolysiloxane (Aa).
  • the content of the organopolysiloxane (Ae) in the composition of the present invention is not particularly limited, but for the reason that the effect of the present invention is more excellent,
  • the content is preferably 1 to 90% by mass, more preferably 10 to 50% by mass, based on the entire composition.
  • the condensation catalyst is not particularly limited as long as it is a catalyst used for the condensation of a silanol group and an alkoxysilyl group.
  • the condensation catalyst can be a metal salt; complex; alcoholate; oxide; multi-metal oxide, salts and / or complexes thereof;
  • the condensation catalyst is preferably a metal salt compound from the viewpoint of excellent room temperature stability and curability.
  • the condensation catalyst can be a compound having a metal (for example, at least one selected from the group consisting of Al, Zn, Sn, Zr, Hf, Ti, and a lanthanoid) and an organic group.
  • the metal can be bonded to the organic group, for example, through a heteroatom such as an oxygen atom, nitrogen atom, sulfur atom, and / or via a linking group such as an ester bond.
  • the organic group includes an aliphatic hydrocarbon group (including chain, branched, cyclic, and combinations thereof.
  • the aliphatic hydrocarbon group can have an unsaturated bond), aromatic hydrocarbon groups, and combinations thereof Is mentioned.
  • the organic group can have a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom.
  • organic group examples include an organic carboxylate (—O—CO—R, where R is a hydrocarbon group); a hydrocarbon group such as an alkoxy group or a phenoxy group bonded to an oxy group (—O— -R: where R is a hydrocarbon group); ligand; combinations thereof.
  • the condensation catalyst is preferably a metal compound containing at least one selected from the group consisting of Al, Zn, Sn, Zr, Hf, Ti and a lanthanoid from the viewpoint of excellent curability and room temperature stability. More preferably, it is a compound.
  • the content of the condensation catalyst in the composition of the present invention is not particularly limited, but for the reason that the effect of the present invention is more excellent, 0.01 to
  • the content is preferably 10% by mass, more preferably 0.1 to 1% by mass.
  • the metal particles (specific metal particles) to which (B) an organic acid is bound contained in the composition of the present invention are not particularly limited as long as they are metal particles to which an organic acid is bound.
  • the specific metal particles can be considered to adsorb sulfur-based gas very efficiently. That is, the specific metal particles are considered to function as a sulfur component adsorbent.
  • the metal component of the specific metal particles include Ag (silver), Cu (copper), Ni (nickel), Co (cobalt), Au (gold), and Pd (palladium). From the reason that the effect of the present invention is more excellent, Ag and Cu are preferable, and Ag is more preferable. That is, the specific metal particles are preferably Ag particles to which an organic acid is bonded.
  • the metal component may be in any form such as a simple substance, a mixture or an alloy. In the present invention, the metal particles are bonded to the organic acid, and the surface of the metal particles is modified. When infrared absorption is measured for such metal particles to which an organic acid is bonded, a peak derived from the bond between the organic acid and the metal is observed in the vicinity of 1518 cm ⁇ 1 .
  • carboxylic acid Although it does not restrict
  • the carboxylic acid include aliphatic carboxylic acids such as myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, paratoylic acid, succinic acid, malonic acid, tartaric acid, malic acid, glutaric acid, adipic acid and acetic acid.
  • Examples thereof include aromatic carboxylic acids such as acid, phthalic acid, maleic acid, isophthalic acid, terephthalic acid, benzoic acid and naphthenic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid.
  • aromatic carboxylic acids such as acid, phthalic acid, maleic acid, isophthalic acid, terephthalic acid, benzoic acid and naphthenic acid
  • alicyclic carboxylic acids such as cyclohexanedicarboxylic acid.
  • aromatic carboxylic acids such as acid, phthalic acid, maleic acid, isophthalic acid, terephthalic acid, benzoic acid and naphthenic acid
  • alicyclic carboxylic acids such as cyclohexanedicarboxylic acid.
  • aliphatic carboxylic acids are preferred (especially aliphatic carboxylic acids having 3 to 30 carbon atoms), and higher aliphatic carboxylic acids (especially alipha
  • Examples of higher aliphatic carboxylic acids include myristic acid, stearic acid, and palmitic acid.
  • the carboxylic acid is preferably an aliphatic carboxylic acid having 15 to 20 carbon atoms, more preferably a saturated aliphatic carboxylic acid having 15 to 20 carbon atoms, for the reason that the effects of the present invention are more excellent. More preferably, it is an acid.
  • the average particle diameter of the specific metal particles is not particularly limited, but is preferably 800 nm or less, more preferably 1 to 800 nm, and even more preferably 1 to 200 nm, because the effects of the present invention are more excellent.
  • an average particle diameter means an average value when the thing without a gap
  • TEM transmission electron microscope
  • the specific metal particles are preferably used as a dispersion because the effect of the present invention is more excellent. Especially, it is preferable to use as a dispersion liquid of a low boiling-point solvent from the reason which the effect of this invention is further excellent.
  • the specific metal particles are used as a low-boiling solvent dispersion, the dispersion serves as a diluent, and the specific metal particles are uniformly dispersed in the composition of the present invention without agglomeration, so the effect of the present invention is more excellent. . Further, the transparency of the cured product is improved.
  • a method for producing a dispersion in which specific metal particles are dispersed in a low-boiling solvent is not particularly limited, but an organic acid metal salt is added to a high-boiling solvent and then heated and mixed for the reason that the effect of the present invention is more excellent. In this way, metal particles (specific metal particles) bonded with an organic acid are formed, and the obtained liquid (dispersion liquid in which specific metal particles are dispersed in a high-boiling solvent) can be separated into a high-boiling solvent and two-phase separation.
  • a method of collecting the low boiling point solvent phase by transferring the specific metal particles into the low boiling point solvent by adding the boiling point solvent is preferable.
  • Organic acid metal salt Specific examples and preferred embodiments of the organic acid and metal component of the organic acid metal salt are as described above. Specific examples of the organic acid metal salt include silver myristate and silver stearate.
  • High boiling point solvent As the high boiling point solvent, glycerin is preferable because the effect of the present invention is more excellent. Furthermore, examples of the high boiling point solvent that can be used with glycerin include glycol solvents such as ethylene glycol, diethylene glycol and polyethylene glycol, and ether solvents such as diethyl ether, and the reason why the effect of the present invention is more excellent. Therefore, ethylene glycol, diethylene glycol, polyethylene glycol and diethyl ether can be preferably used.
  • the low boiling point solvent is a solvent having a boiling point smaller than that of the high boiling point solvent and capable of two-phase separation from the high boiling point solvent.
  • Specific examples of the low boiling point solvent include toluene, methyl isobutyl ketone, and methyl ethyl ketone.
  • the difference between the SP value (solubility parameter) of the low boiling point solvent and the SP value of the organic acid in the specific metal particles is preferably small. Thereby, the extractability of the specific metal particles from the high-boiling solvent is improved, and it becomes easier to remove the high-boiling solvent together with by-products and residues.
  • the boiling point of the low-boiling solvent is preferably 40 to 120 ° C. from the viewpoint of moldability and handleability of a cured product (eg, a sealing material and a protective layer).
  • a method for dispersing the specific metal particles in the dispersion is not particularly limited, but a stirring disperser having blades such as a propeller blade, a turbine blade and a paddle blade, a mill type disperser such as a ball mill, a bead mill and a colloid mill, a homogenizer, A sonic homogenizer, a high-pressure homogenizer, and the like can be suitably used.
  • the content of the specific metal particles in the dispersion in which the specific metal particles are dispersed in the low-boiling solvent described above is not particularly limited, but from the viewpoint of moldability and dispersibility, 0.05 to The amount is preferably 5 parts by mass, more preferably 0.1 to 3 parts by mass.
  • the content of the specific metal particles is not particularly limited, but for the reason that the effect of the present invention is more excellent, as a metal with respect to 100 parts by mass of the above-mentioned (A) curable silicone resin composition (
  • it is preferably 1 to 500 ppm by mass (as Ag) ( ⁇ 10 ⁇ 6 parts by mass), more preferably 5 to 200 ppm by mass, and even more preferably 10 to 100 ppm by mass.
  • the composition of the present invention is within a range that does not impair the object of the present invention, for example, a curing retarder, an ultraviolet absorber, a filler (particularly silica), an anti-aging agent, an antistatic agent, a flame retardant, an adhesion promoter, It may further contain additives such as a dispersant, an antioxidant, an antifoaming agent, a matting agent, a light stabilizer, a dye and a pigment. Of these additives, silica is preferably used as a filler.
  • the type of silica is not particularly limited, and examples thereof include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, and aluminum silicate.
  • the composition of the present invention may further contain a curing retarder.
  • the curing retarder is a component for adjusting the curing rate and working life of the composition of the present invention.
  • the curing retarder is a component for adjusting the curing rate and working life of the composition of the present invention.
  • 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyne Alcohol derivatives having a carbon-carbon triple bond such as -3-ol, phenylbutynol, 1-ethynyl-1-cyclohexanol; 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexene
  • Enyne compounds such as -1-yne; low molecular weight siloxanes containing alkenyl groups such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; methyl-tris (3-
  • the content of the curing retarder is not particularly limited, but is preferably 0.00001 to 0.1 parts by mass with respect to 100 parts by mass of the entire composition of the present invention, and 0.0001 More preferably, it is -0.01 parts by mass.
  • the manufacturing method of the composition of this invention is not specifically limited, For example, the method of manufacturing by mixing the essential component mentioned above and an arbitrary component is mentioned.
  • a method for obtaining a cured product by curing the composition of the present invention is not particularly limited, and examples thereof include a method of heating the composition of the present invention at 80 to 200 ° C. for 10 to 720 minutes.
  • the composition of the present invention is, for example, in the field of display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, semiconductor integrated circuit peripheral materials, etc. It can be used as a primer, a sealing material and the like. Especially, the composition of this invention can be used conveniently for the sealing material and protective layer of LED.
  • the optical semiconductor to which the composition of the present invention can be applied is not particularly limited, and examples thereof include a light emitting diode (LED), an organic electroluminescent element (organic EL), a laser diode, and an LED array.
  • the laminate of the present invention is a laminate used for a semiconductor package, and includes a corrosive base material (for example, a member including silver plating) and a silicone resin layer that covers the corrosive base material.
  • the silicone resin layer is a cured product of the composition of the present invention described above.
  • the silicone resin layer may be coated directly or indirectly with silver plating, but is preferably coated directly.
  • the total light transmittance of the silicone resin layer is preferably 60% or more, and more preferably 80% or more.
  • the upper limit of the total light transmittance of the silicone resin layer is not particularly limited and is 100%.
  • FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention.
  • the laminate 100 includes a corrosive base material (member including silver plating) 120 and a silicone resin layer 102 that covers the corrosive base material 120.
  • the silicone resin layer 102 is a cured product of the above-described composition of the present invention. Since the composition of this invention is excellent in sulfidation resistance, the corrosive base material in the laminated body of this invention cannot sulfidize easily.
  • FIG. 2 is a cross-sectional view schematically showing another example of the laminate of the present invention.
  • the laminate 200 includes a corrosive base material (member including silver plating) 220, an optical semiconductor 203, and a silicone resin layer 202 that indirectly covers the silver plating of the corrosive base material 220.
  • the silicone resin layer 202 is a cured product of the above-described composition of the present invention.
  • the laminate 200 can further include a transparent layer (not shown) between the optical semiconductor 203 and the silicone resin layer 202. Examples of the transparent layer include a resin layer, a glass layer, and an air layer.
  • the optical semiconductor package of the present invention (hereinafter also referred to as “the optical semiconductor sealed body of the present invention”) is obtained by sealing an optical semiconductor element using the composition of the present invention.
  • the optical semiconductor element contains silver.
  • the optical semiconductor element includes, for example, an optical semiconductor and a frame having a recess, the optical semiconductor is disposed at the bottom of the recess, and the frame includes a reflector containing silver on a side surface of the recess. Is mentioned.
  • a semiconductor sealing body of this invention it is provided with the said semiconductor element and a sealing material, and the said sealing material is the hardened
  • FIG. 3 is a cross-sectional view schematically showing an example of the optical semiconductor package (encapsulated optical semiconductor) of the present invention.
  • the optical semiconductor sealing body 300 includes an optical semiconductor 303, a frame 304 having a recess 302, and a sealing material 308, and the optical semiconductor 303 is disposed at the bottom (not shown) of the recess 302.
  • the frame 304 includes a reflector 320 containing silver on the side surface (not shown) of the recess 302, and the sealing material 308 seals the optical semiconductor 303 and the reflector 320.
  • the sealing material 308 is a cured product of the composition of the present invention.
  • the concave portion 302 may be filled with the cured product up to the shaded portion 306.
  • the portion denoted by reference numeral 308 may be another transparent layer, and the hatched portion 306 may be a cured product of the composition of the present invention.
  • the sealing material can contain a fluorescent substance or the like.
  • One optical semiconductor encapsulant can have one or a plurality of optical semiconductors.
  • the optical semiconductor may be disposed in the frame with the light emitting layer (the surface opposite to the surface in contact with the mount member) facing up.
  • the optical semiconductor 303 is disposed on the bottom (not shown) of the recess 302 formed from the frame 304 and the substrate 310, and is fixed by the mount member 301.
  • the end portions 312 and 314 included in the frame body 304 are integrally coupled, and the reflector forms a side surface and a bottom portion.
  • an optical semiconductor can be disposed on the bottom of the reflector.
  • the reflector 320 may have a tapered opening end (not shown) whose cross-sectional dimension increases as the distance from the bottom (not shown) of the recess 302 increases.
  • Examples of the mounting member include silver paste and resin.
  • Each electrode (not shown) of the optical semiconductor 303 and the external electrode 309 are wire bonded by a conductive wire 307.
  • the optical semiconductor sealing body 300 can seal the concave portion 302 with a sealing material 308, 306, or 302 (a portion in which the portion 308 and the portion 306 are combined).
  • a sealing material 308, 306, or 302 a portion in which the portion 308 and the portion 306 are combined.
  • FIG. 4 is a cross-sectional view schematically showing another example of the optical semiconductor package (optical semiconductor sealed body) of the present invention.
  • the optical semiconductor sealing body 400 has a lens 401 on the optical semiconductor sealing body 300 shown in FIG.
  • the lens 401 may be a cured product of the composition of the present invention.
  • FIG. 5 is a cross-sectional view schematically showing another example of the optical semiconductor package (encapsulated optical semiconductor) of the present invention.
  • an optical semiconductor sealing body 500 includes an optical semiconductor 503, a substrate 510 including a frame having a recess, and a sealing material 502, and the optical semiconductor 503 is disposed at the bottom of the recess.
  • the sealing material 502 seals the optical semiconductor 503 and the reflector 520.
  • a frame (not shown) and the substrate 510 can be integrally formed.
  • the reflector 520 may be formed integrally with the side surface and the bottom (not shown) of the recess.
  • the optical semiconductor 503 is fixed on the substrate 510 with a mount member 501. Examples of the mount member include silver paste and resin.
  • Each electrode (not shown) of the optical semiconductor 503 is wire-bonded by a conductive wire 507.
  • the resin 506 may be a cured product of the composition of the present invention.
  • FIG. 6 is a diagram schematically showing an example of an LED display using the composition of the present invention and / or the optical semiconductor package (optical semiconductor sealing body) of the present invention.
  • an LED display 600 includes an optical semiconductor sealing body 601 arranged in a matrix in a housing 604, and the optical semiconductor sealing body 601 is sealed with a sealing material 606.
  • the light shielding member 605 is arranged in the part.
  • the composition of the present invention can be used for the sealing material 606.
  • the optical semiconductor sealing body of the present invention can be used as the optical semiconductor sealing body 601.
  • Examples of the use of the laminated body of the present invention or the optical semiconductor package (semiconductor encapsulated body) of the present invention include, for example, automotive lamps (head lamps, tail lamps, directional lamps, etc.), household lighting fixtures, industrial lighting fixtures, Stage lighting fixtures, displays, signals, projectors.
  • ⁇ Total light transmittance> The obtained curable resin composition was poured into silicone rubber (thickness: 1 mm) hollowed in a U-shape, sandwiched between glass plates and cured (100 ° C. for 1 hour, then 150 ° C. for 2 hours). The total light transmittance was measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory). The results are shown in Table 1. As a sealing material use, it is preferable that it is 80% or more.
  • Organopolysiloxane A-a1 PMV-9225 (both end vinyl group methylphenyl polysiloxane, manufactured by Amax)
  • Organopolysiloxane Aa2 polysiloxane represented by average unit formula (PhSiO 3/2 ) 0.75 (ViMe 2 SiO 1/2 ) 0.25 (manufactured by Yokohama Rubber Co., Ltd.)
  • Organopolysiloxane Ab2 polysiloxane represented by average unit formula (PhSiO 3/2 ) 0.60 (HMe 2 SiO 1/2 ) 0.40 (manufactured by Yokohama Rubber Co., Ltd.) Hydrosilylation catalyst Ac:
  • the specific metal particle dispersion B-1 was prepared as follows. Silver stearate 5.56g and saccharin 0.56g were added to glycerol 1000g, and it heat-stirred at 150 degreeC for 15 minutes, and cooled to 80 degreeC. The obtained liquid was added to 1 kg of methyl isobutyl ketone (extraction solvent) and stirred at room temperature. After standing for 24 hours, the methyl isobutyl ketone layer was collected to obtain a methyl isobutyl ketone dispersion of silver particles.
  • the average particle diameter was measured about the silver particle in the obtained dispersion liquid. Specifically, 1 g of the dispersion obtained in 10 g of toluene was dropped, and the average particle size was measured by a dynamic light scattering method (Zeta potential / particle size measurement system manufactured by Otsuka Electronics Co., Ltd.). As a result, the scattering intensity distribution shown in FIG. 7 was obtained, and it was found that the average particle diameter of the silver particles in the dispersion was 301.7 nm.
  • Dispersion B-2 of specific metal particles SV-001 (dispersion of silver particles bonded with stearic acid, manufactured by Toago Materials Technology Co., Ltd.)
  • the specific metal particle dispersion B-2 was prepared by the same method except that the methyl isobutyl ketone (extraction solvent) used in the specific metal particle dispersion B-1 was changed to toluene.
  • the average particle diameter of the silver particles in the obtained dispersion was measured, the same result as that of the dispersion B-1 of the specific metal particles was obtained.
  • specific metal particle content represents ppm parts by mass ( ⁇ 10 ⁇ 6 parts by mass) as Ag of specific metal particles with respect to 100 parts by mass of the curable silicone resin composition.
  • 16 parts of the specific metal particles (B-1) are added to 100 parts by mass of the curable silicone resin composition (Aa1, Aa2, Ab1, Ab2, and Ac). Contains 1 ⁇ 10 ⁇ 6 parts by mass.
  • Si—H / Si—Vi molar ratio represents the “Si—H / Si—Vi molar ratio” described above.
  • Examples 1 to 8 containing specific metal particles all exhibited excellent resistance to sulfidation.
  • Examples 1 to 5 and 8 in which the content of the specific metal particles was 100 ppm by mass or less as a metal with respect to 100 parts by mass of the curable silicone resin composition showed excellent permeability.
  • Comparative Examples 1 and 2 not containing specific metal particles had insufficient sulfidation resistance.
  • Optical semiconductor 300 100, 200 Laminated body 102, 202 Silicone resin layer 120, 220 Corrosive base material 203 Optical semiconductor 300, 400, 500 Sealed optical semiconductor body 301, 501 Mount member 302 Recess 303, 503 Optical semiconductor 304 Frame body 306 Shaded portion 307 , 507 Conductive wire 308, 502 Encapsulant 7 309 External electrode 312, 314 End 310, 510 Substrate 320, 520 Reflector 401 Lens 505 Inner lead 506 Resin 600 LED display 601 Optical semiconductor sealing body 604 Housing 605 Light shielding member 606 Sealing material

Landscapes

  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Led Device Packages (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le but de la présente invention est de proposer : une composition de résine durcissable qui permet à un boîtier de semi-conducteur optique d'avoir une excellente résistance à la sulfuration dans les cas où cette composition de résine durcissable est utilisée en tant que matériau d'étanchéité pour un élément semi-conducteur optique ; un stratifié qui comprend un placage d'argent et un produit durci de cette composition de résine durcissable ; et un boîtier de semi-conducteur optique qui est obtenu par scellement d'un élément semi-conducteur optique en utilisant cette composition de résine durcissable. Une composition de résine durcissable selon la présente invention contient (A) une composition de résine de silicone durcissable et (B) des particules métalliques auxquelles un acide organique est lié.
PCT/JP2018/010739 2017-03-23 2018-03-19 Composition de résine durcissable, stratifié et boîtier de semi-conducteur optique WO2018173996A1 (fr)

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JP2006328302A (ja) * 2005-05-30 2006-12-07 Ge Toshiba Silicones Co Ltd 導電性シリコーンゴム組成物及び導電材料
JP2008303233A (ja) * 2007-06-05 2008-12-18 Momentive Performance Materials Japan Kk 高導電性充填剤及びそれを用いた高導電性シリコーン組成物
JP2012046699A (ja) * 2010-08-30 2012-03-08 Toyo Seikan Kaisha Ltd 吸着性シリコーン樹脂組成物及びその製造方法
JP2012077248A (ja) * 2010-10-05 2012-04-19 Toyo Seikan Kaisha Ltd 銀含有樹脂組成物及びその製造方法
JP2012077247A (ja) * 2010-10-05 2012-04-19 Toyo Seikan Kaisha Ltd 銀含有樹脂組成物及びその製造方法
WO2012067153A1 (fr) * 2010-11-17 2012-05-24 横浜ゴム株式会社 Composition de résine silicone, ainsi que structure contenant une résine silicone, corps d'étanchéité pour élément semi-conducteur optique et procédé de mise en oeuvre de composition de résine silicone associés
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JP2013241643A (ja) * 2012-05-18 2013-12-05 Toyo Seikan Group Holdings Ltd 銀超微粒子含有分散液及びその製造方法
JP2014214209A (ja) * 2013-04-25 2014-11-17 信越化学工業株式会社 導電性シリコーンゴム組成物
WO2015064700A1 (fr) * 2013-10-30 2015-05-07 東洋製罐グループホールディングス株式会社 Liquide de dispersion contenant des particules métalliques antibactériennes ultrafines et son procédé de production
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