WO2013027640A1 - Composition à base d'acrylate - Google Patents

Composition à base d'acrylate Download PDF

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Publication number
WO2013027640A1
WO2013027640A1 PCT/JP2012/070763 JP2012070763W WO2013027640A1 WO 2013027640 A1 WO2013027640 A1 WO 2013027640A1 JP 2012070763 W JP2012070763 W JP 2012070763W WO 2013027640 A1 WO2013027640 A1 WO 2013027640A1
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WIPO (PCT)
Prior art keywords
meth
group
component
acrylate
mass
Prior art date
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PCT/JP2012/070763
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English (en)
Japanese (ja)
Inventor
猛 岩崎
大地 小川
勇人 山崎
寛 小幡
智明 武部
東洋藏 藤岡
友良 村上
Original Assignee
出光興産株式会社
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Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Priority to CN201280040391.9A priority Critical patent/CN103732640A/zh
Priority to KR1020147004158A priority patent/KR20140051958A/ko
Publication of WO2013027640A1 publication Critical patent/WO2013027640A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/048—Polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a composition containing an acrylate compound, and more particularly to a composition suitably used as a raw material for a sealing material, an optical material and the like, and a cured product thereof.
  • optical semiconductor devices each having a light-emitting element with an LED (light-emitting diode) chip having a pn bond formed by a semiconductor layer grown on a crystal substrate and using this junction region as a light-emitting layer Widely used in display devices and display devices.
  • this optical semiconductor device include a visible light emitting device and a high-temperature operating electronic device using a gallium nitride compound semiconductor such as GaN, GaAlN, InGaN, and InAlGaN. Recently, blue light emitting diodes and ultraviolet light emitting diodes are used. Development is progressing in this field.
  • An optical semiconductor device including an LED chip as a light emitting element includes an LED chip mounted on a light emitting surface side of a lead frame, and electrically connecting the LED chip and the lead frame by wire bonding. It is sealed with a resin that also functions as a lens.
  • White LEDs have attracted attention as a new light source and are used for lighting applications and the like.
  • White LED is a type in which YAG phosphor is coated on a GaN bare chip, and GaN blue light emission and yellow light emission of GaN are mixed to emit white light, and red, green and blue chips are packaged in one package to emit white light.
  • a method for combining a plurality of phosphor materials using an ultraviolet LED chip as a light source has been developed for improving the color tone. Furthermore, in order to use LED for illumination use etc., improving its durability is calculated
  • an epoxy resin is used as a sealing material used when sealing a light emitting element such as an LED (light emitting diode) chip.
  • an epoxy resin is used due to factors such as good transparency and workability.
  • most epoxy resins for sealing LEDs are composed of bisphenol A glycidyl ether and methylhexahydrophthalic anhydride, an amine-based or phosphorus-based curing accelerator.
  • these components generate carbonyl groups by absorption of ultraviolet light, they have the disadvantage of absorbing visible light and turning yellow.
  • Silicone resins are widely used to improve yellowing due to ultraviolet light and brightness reduction.
  • the silicone resin has a problem that the light extraction efficiency is low because the refractive index is low, and the adhesion with the lead frame and the reflecting material is poor because the polarity is low.
  • soldering by a reflow soldering method is performed. In the reflow furnace, since it is exposed to heat at 260 ° C. for about 10 seconds, the conventional epoxy resin or silicone resin may be deformed or cracked by heat.
  • Patent Document 1 proposes a transparent sealing material for an optical semiconductor that provides a cured product that is stable against ultraviolet rays and heat, hardly causes yellowing, and has excellent adhesion. ing.
  • cured material may be inferior to adhesiveness with the surrounding base materials (reflecting material resin or a metal frame).
  • the present inventors have found in Patent Document 2 that the adhesiveness to the substrate can be improved by a composition containing a specific (meth) acrylate compound and a radical polymerization initiator.
  • a cured product obtained by curing the composition disclosed in Patent Document 2 is subjected to a thermal shock test performed as a reliability evaluation in the field of optical semiconductors (exposing a semiconductor repeatedly in an environment of extremely low temperature and high temperature alternately). In the test), there may be a problem that the gold wire connecting the light emitting element and the lead frame is broken, and the reliability is not sufficiently satisfied.
  • optical semiconductors emit light from minute light emitting elements, the spread of light is small compared to fluorescent lamps, and there is a need to scatter emitted light as much as possible in applications such as lighting.
  • the transparent cured product disclosed in 2 cannot satisfy this requirement.
  • the present invention has been made in view of the above circumstances, and is a composition that is suitably used as a raw material for a sealing material, and breaks a gold wire in a thermal shock test while maintaining a conventional level regarding heat resistance and adhesion.
  • An object of the present invention is to provide a composition that gives a cured product that does not cause defects and can simultaneously scatter light emitted from an optical semiconductor.
  • the present invention provides the following 1 to 8. 1.
  • a composition comprising an initiator and (E) silica-based fine particles having an average particle diameter of 0.1 to 500 ⁇ m, or silica-based fibers having an average fiber diameter
  • the component (A) is an alkyl (meth) acrylate having an alkyl group having 12 or more carbon atoms selected from hydrogenated polybutadiene di (meth) acrylate and hydrogenated polyisoprene (meth) acrylate, and / or the number average molecular weight 400 2.
  • the component (C) includes a hydroxyl group, an epoxy group, a glycidyl ether group, a tetrahydrofurfuryl group, an isocyanate group, a carboxyl group, an alkoxysilyl group, a phosphate ester group, a lactone group, an oxetane group, a tetrahydropyranyl group, and an amino group.
  • the amount of component (A) is 10 to 90% by mass, the amount of component (B) is 5 to 89.5% by mass, (C
  • the amount of the component (D) is 0.5 to 50% by mass, and the amount of the component (D) is 0.01 to 10 with respect to a total of 100 parts by mass of the component (A), the component (B) and the component (C).
  • the sealing material according to 7 above which is for an optical semiconductor or a light receiving element.
  • composition suitably used as a raw material for a sealing material and the like, while maintaining the conventional level with respect to heat resistance and adhesiveness, no disconnection failure of a gold wire in a thermal shock test occurs. Also provided is a composition that provides a cured product that can simultaneously scatter light emitted from an optical semiconductor.
  • composition of the present invention is selected from (A) (meth) acrylate-modified silicone oil, alkyl (meth) acrylate having an alkyl group having 12 or more carbon atoms, and polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more.
  • (meth) acrylate compounds (B) (meth) acrylate compounds in which an alicyclic hydrocarbon group having 6 or more carbon atoms is ester-bonded, (C) (meth) acrylic acid or (meth) acrylate having a polar group A compound, (D) a radical polymerization initiator, and (E) silica-based fine particles having an average particle diameter of 0.1 to 500 ⁇ m, or silica-based fibers having an average fiber diameter and a fiber length of 0.1 to 500 ⁇ m.
  • (meth) acrylate refers to acrylate and / or methacrylate. The same applies to other similar terms.
  • the component (A) used in the present invention is a (meth) acrylate-modified silicone oil, an alkyl (meth) acrylate having an alkyl group having 12 or more carbon atoms (hereinafter also referred to as “long-chain alkyl (meth) acrylate”) and a number average It is one or more (meth) acrylate compounds selected from polyalkylene glycol (meth) acrylates having a molecular weight of 400 or more.
  • the (meth) acrylate-modified silicone oil of component (A) is a compound having an acryl group and / or a methacryl group at the end and containing a dialkylpolysiloxane in the skeleton.
  • the (meth) acrylate-modified silicone oil of component (A) is a modified product of dimethylpolysiloxane in many cases, but the alkyl in the dialkylpolysiloxane skeleton is replaced with a methyl group or an alkyl group other than a methyl group. All or some of the groups may be substituted. Examples of the alkyl group other than the methyl group include an ethyl group and a propyl group.
  • polydialkylsiloxane having an acryloxyalkyl terminal or a methacryloxyalkyl terminal can be used.
  • (3-acryloxy-2-hydroxypropyl) -terminated polydimethylsiloxane and acryloxy-terminated ethylene oxide dimethylsiloxane-ethylene oxide ABA block copolymer are preferably used because of transparency after curing.
  • the long-chain alkyl (meth) acrylate as the component (A) is a (meth) acrylate containing an alkyl group having 12 or more carbon atoms.
  • the alkyl group having 12 or more carbon atoms include dodecyl group, lauryl group, tetradecyl group, hexadecyl group, octadecyl group (including stearyl group), eicosyl group, triacontyl group and tetracontyl group.
  • the alkyl group having 12 or more carbon atoms may be an alkyl group derived from a hydride of a polymer such as polybutadiene or polyisoprene. Excellent adhesion can be obtained by using a long-chain alkyl (meth) acrylate.
  • the long-chain alkyl (meth) acrylate include hydrogenated polybutadiene such as hydrogenated polybutadiene di (meth) acrylate and hydrogenated polyisoprene (meth) acrylate, and acrylic or methacrylic compounds having a hydrogenated polyisoprene skeleton, or Examples include stearyl methacrylate.
  • hydrogenated polybutadiene di (meth) acrylate and hydrogenated polyisoprene di (meth) acrylate are preferable in terms of adhesion.
  • the polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more as the component (A) is polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, ethoxylated trimethylol. Examples thereof include propane tri (meth) acrylate and ethoxylated pentaerythritol tetra (meth) acrylate.
  • a polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more excellent toughness and adhesion can be obtained.
  • the maximum value of the number average molecular weight is not particularly limited, but a number average molecular weight of 10,000 or less is preferable from the viewpoint of compatibility with the component (B).
  • At least one selected from the (meth) acrylate-modified silicone oils at least one selected from the long-chain alkyl (meth) acrylates, or the number average molecular weight of 400 or more.
  • At least one selected from polyalkylene glycol (meth) acrylates of the above, or the above-mentioned (meth) acrylate-modified silicone oil, long-chain alkyl (meth) acrylate, and polyalkylene glycol having a number average molecular weight of 400 or more You may choose and combine suitably from (meth) acrylate.
  • a long-chain alkyl (meth) acrylate selected from hydrogenated polybutadiene di (meth) acrylate and hydrogenated polyisoprene di (meth) acrylate, and / or a polyalkylene glycol (meth) acrylate having a number average molecular weight of 400 or more is preferable. .
  • the content of the component (A) in the composition of the present invention is usually 10 to 90% by mass, preferably 15 to 80% by mass, based on the sum of the components (A), (B) and (C). is there.
  • the adhesiveness and toughness which were excellent by making (A) component 10 mass% or more are obtained.
  • the component (B) used in the present invention is a (meth) acrylate compound in which an alicyclic hydrocarbon group having 6 or more carbon atoms is ester-bonded.
  • the alicyclic hydrocarbon group having 6 or more carbon atoms in the component (B) includes a cyclohexyl group, 2-decahydronaphthyl group, adamantyl group, 1-methyladamantyl group, 2-methyladamantyl group, biadamantyl group, dimethyladamantyl group Group, norbornyl group, 1-methyl-norbornyl group, 5,6-dimethyl-norbornyl group, isobornyl group, tetracyclo [4.4.0.1 2,5 .
  • the (meth) acrylate compound of the component (B) the (meth) acrylate having the alicyclic hydrocarbon group, for example, cyclohexyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, Isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc. are mentioned.
  • the component (B) one type of the (meth) acrylate compound may be used, or two or more types may be used in combination.
  • excellent heat resistance can be obtained by using an alicyclic hydrocarbon group having 6 or more carbon atoms.
  • the ester substituent is an alicyclic hydrocarbon group and does not contain aromatics, it is difficult to cause deterioration due to ultraviolet rays.
  • the content of the component (B) in the composition of the present invention is usually 5 to 89.5% by mass, preferably 10 to 80% by mass, based on the sum of the components (A), (B) and (C). %.
  • the content of the component (B) in the composition of the present invention is usually 5 to 89.5% by mass, preferably 10 to 80% by mass, based on the sum of the components (A), (B) and (C). %.
  • the component (C) used in the present invention is (meth) acrylic acid or a (meth) acrylate compound having a polar group. Since the component (C) has polarity, it forms a hydrogen bond with a metal surface having polarity in the same manner, thereby improving adhesion. Further, the wettability is improved by the presence of the polar group.
  • an alkylene glycol group may be concerned with adhesion
  • Examples of (meth) acrylate compounds having polar groups include (meth) acrylate compounds in which polar groups containing atoms other than carbon and hydrogen are ester-bonded.
  • Examples of polar groups include hydroxyl groups, epoxy groups, glycidyl ether groups, tetrahydro groups. Examples include a furfuryl group, an isocyanate group, a carboxyl group, an alkoxysilyl group, a phosphate ester group, a lactone group, an oxetane group, a tetrahydropyranyl group, and an amino group.
  • At least one selected from the (meth) acrylic acid or at least one selected from the (meth) acrylate compounds having the polar group may be used. Or you may select and combine suitably from the said (meth) acrylic acid and the (meth) acrylate compound which has a polar group.
  • the content of component (C) in the composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40% by mass, based on the total of component (A), component (B) and component (C). %.
  • component (C) is 0.5% by mass or more, excellent adhesion to a resin material or a metal material that comes into contact with the encapsulant when the optical semiconductor is encapsulated is exhibited.
  • C By making content of a component into 50 mass% or less, a balance with another component becomes favorable.
  • ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide, Diacyl peroxides such as benzoyl peroxide and m-toluyl benzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bi (T-butylperoxy) hexane, 1,3-bis (t-
  • a radical photopolymerization initiator can also be used as the component (D).
  • photo radical polymerization initiators include Irgacure 651 (Irgacure 651), Irgacure 184 (Irgacure 184), Darocur 1173 (DAROCUR1173), Irgacure 2959 (Irgacure 2959), Irgacure 127 (Irgacure 127), Irgacure 127 g Irgacure 379 (Irgacure 379), Darocur TPO (DAROCUR TPO), Irgacure 819 (Irgacure 819), Irgacure 784 (Irgacure 784) (above, BASF Japan Ltd., trademark), etc. are mentioned.
  • the radical polymerization initiator of component (D) may be used alone or in combination of two or more.
  • the content of the component (D) in the composition of the present invention is usually 0.01 to 10 parts by mass, preferably 100 parts by mass with respect to a total of 100 parts by mass of the components (A), (B) and (C), preferably 0.1 to 5.0 parts by mass.
  • silica-based fine particles or silica-based fibers In the present invention, silica-based fine particles having an average particle diameter of 0.1 to 500 ⁇ m or silica-based fibers having an average fiber diameter and fiber length of 0.1 to 500 ⁇ m are used as the component (E).
  • the silica-based fine particles or silica-based fibers of the component (E) are fine particles mainly composed of silicon dioxide, and the shape thereof is not limited, such as spherical, fibrous, rod-like, plate-like, and irregular shapes. .
  • silica-based fine particles or silica-based fibers are generally silica powder, silica beads, (true) spherical silica, fused silica, fused spherical silica, crystalline silica, glass powder, glass beads, glass filler, What is called glass fiber, milled glass fiber, talc, whisker or the like can be used.
  • silica soda lime glass, low alkali glass, borosilicate glass, sodium borosilicate glass, aluminoborosilicate glass, quartz glass, E glass, T glass, C glass, S What is called by name, such as glass and AR glass, is mentioned.
  • silica-based fine particles or silica-based fibers of the component (E) may be performed, and examples of the surface treatment include alkylation treatment, trimethylsilylation treatment, silicone treatment, and treatment with a coupling agent.
  • the treatment with the coupling agent include amino silane treatment, (meth) acryl silane treatment, vinyl silane treatment, and the like, among which (meth) acryl silane treatment is preferable.
  • These silica-based fine particles or silica-based fibers may be used alone or in combination of two or more. Further, silica-based fine particles and silica-based fibers may be used in combination.
  • the average particle diameter of the silica-based fine particles (E) or the average fiber diameter and fiber length of the silica-based fibers is 0.1 to 500 ⁇ m. If the average particle diameter of the silica-based fine particles of component (E) or the average fiber diameter and fiber length of silica-based fibers are within this range, sedimentation in the composition liquid of component (E) can be suppressed. When the average particle diameter of the silica-based fine particles of component (E), or the average fiber diameter and fiber length of the silica-based fibers exceeds 500 ⁇ m, precipitation of the acrylate composition in the liquid is accelerated, and transfer molding and compression molding are performed. When producing a cured product, the gate of the mold may be blocked.
  • the average particle diameter of the silica-based fine particles of the component (E) or the average fiber diameter and fiber length of the silica-based fibers is less than 0.1 ⁇ m, it is difficult to disperse the aggregate of the component (E).
  • an organic surface treatment is applied to impart dispersibility to the system composition, discoloration due to heat of the cured product may be promoted.
  • the viscosity increase due to thixotropy is likely to occur, and as an effect of the present invention, if an attempt is made to add a sufficient amount of the component (E) to suppress the occurrence of defective disconnection of the gold wire in the thermal shock test, The liquid may not flow.
  • the average particle diameter of the silica-based fine particles of component (E) or the average fiber diameter and fiber length of the silica-based fibers is small, light emission from the optical semiconductor element is likely to be scattered, and if large, the straightness of light emission is increased. be able to.
  • the average particle diameter of the silica-based fine particles of component (E), or the average fiber diameter and fiber length of the silica-based fibers is preferably 0.2 to 200 ⁇ m, more preferably 0.5 to 100 ⁇ m. is there.
  • the average particle size of fine particles refers to a number average value obtained by observing particles using an electron microscope and measuring the particle size of 100 primary particles.
  • the particle diameter is the diameter of the primary particle when the shape of the particle is spherical, and is the average value of the major axis and the minor axis of the primary particle when the particle has a shape other than the spherical shape.
  • the silica-based fine particles or silica-based fibers of the component (E) can be suitably used for the composition of the present invention because the refractive index is close to the cured product of the acrylate-based composition. If the refractive index difference between the silica-based fine particles of component (E) or silica-based fibers and the cured resin is large, the transparency of the cured product is impaired and the amount of light emitted from the optical semiconductor element is reduced. Conversely, a transparent cured product can be obtained if the refractive index of the silica-based fine particles or silica fibers of the component (E) and the cured resin are matched in the entire visible light region.
  • the content of the component (E) in the composition of the present invention is 5 to 500 parts by mass, preferably 10 to 100 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C). 400 parts by mass, more preferably 20 to 200 parts by mass.
  • the content of the component (E) is less than 5 parts by mass, the effect in the present invention cannot be obtained, and when it exceeds 500 parts by mass, the fluidity of the composition is lowered and the liquid state cannot be maintained.
  • the toughness of the cured product may decrease.
  • the composition of the present invention may contain inorganic particles and phosphors as the component (F) as needed, as long as the effects of the present invention are not impaired.
  • inorganic particles can be used. Specific examples thereof include silica particles (excluding (E) component) such as quartz, silicic anhydride, fused silica and crystalline silica, alumina, zirconia, titanium oxide and the like. Can be mentioned.
  • silica particles excluding (E) component
  • inorganic particles and the like that are used or proposed as fillers for conventional sealing materials such as epoxy resins.
  • the inorganic particles may be appropriately subjected to a surface treatment, for example, the same surface treatment as that exemplified for the component (E).
  • YAG fluorescent substance, silicate fluorescent substance, etc. can be used as fluorescent substance for white LED.
  • Component (F) inorganic particles and phosphors may be used singly or in combination of two or more. The content thereof is usually 1 to 100 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C).
  • composition of the present invention one or more other (meth) acrylate compounds [(meth) acrylate compounds other than the components (A) to (C)] are added as the component (G) for imparting strength.
  • Component (meth) acrylate compounds include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, neopentyldiol di (meth) acrylate, polyethylene glycol di (meth) acrylate having a number average molecular weight of less than 400, polypropylene glycol di (meth) acrylate, methoxypolyethylene methacrylate, etc.
  • Component (meth) acrylate compounds may be used alone or in combination of two or more.
  • the content is usually 100 parts by mass or less, preferably 50 parts by mass or less, with respect to 100 parts by mass in total of the component (A), the component (B) and the component (C).
  • antioxidants for example, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, vitamin antioxidants, lactone antioxidants, amine antioxidants, and the like.
  • phenolic antioxidants examples include Irganox 1010 (Irganox 1010), Irganox 1076 (Irganox 1076), Irganox 1330 (Irganox 1330), Irganox 3114 (Irganox 3114), Irganox 3125 (Irganox 3125), Irganox 3190 (Irganox 3190), Irganox 3190 (Trademark), BHT, Cyanox 1790 (Cyanox 1790, Cyanamid Co., Ltd.), and commercializers such as Sumilizer GA-80 (Sumitizer GA-80, Sumitomo Chemical Co., Ltd.).
  • Examples of phosphorus antioxidants include Irgafos 168 (Irgafos 168), Irgafos 12 (Irgafos 12), Irgafos 38 (trade name, BASF Japan Ltd.), Adekastab 329K (ADKSTAB329K), Adekastab PEP36 (ADPSTAB) PEP-8 (ADKSTAB PEP-8) (above, ADEKA Corporation, trademark), Sardstab P-EPQ (Clariant, trademark), Weston 618 (Weston 618), Weston 619G (Weston 619G), Weston-624 Examples include commercial products such as (Weston-624) (general electric company, trademark).
  • sulfur-based antioxidant examples include DSTP (Yoshitomi), DLTP (Yoshitomi), DLTOIB, DMTP (Yoshitomi) (above, API Corporation, trademark), Seenox 412S (Sipro Kasei Corporation, trademark), Cyanox 1212. (Commercially available from Cyanamid Co., Ltd.) and commercializers such as Sumilizer TP-D (Sumilizer TP-D, Sumitomo Chemical Co., Ltd.).
  • vitamin antioxidants examples include tocopherol, Irganox E201 (Irganox E201, BASF Japan Ltd., trademark, compound name; 2,5,7,8-tetramethyl-2 (4 ′, 8 ′, 12′-trimethyltridecyl) ) Coumarone-6-ol) and other commercial products.
  • lactone antioxidant those described in JP-A-7-233160 and JP-A-7-247278 can be used. Further, there is HP-136 (BASF Japan Ltd., trademark, compound name; 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one).
  • amine-based antioxidants examples include commercially available products such as Irgas Tab FS042 (BASF Japan Ltd., trademark), GENOX EP (Crampton Corporation, trademark, compound name: dialkyl-N-methylamine oxide).
  • antioxidants may be used alone or in combination of two or more.
  • the content is usually 0.005 to 5 parts by mass, preferably 0.02 to 2 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C).
  • the light stabilizer those generally known can be used, but a hindered amine light stabilizer is preferred.
  • the product names include ADK STAB LA-52, LA-57, LA-62, LA-63, LA-67, LA-68, LA-77, LA-82, LA- from Adeka Co., Ltd. 87, LA-94, Tinuvin 123, 144, 440, 662 from CSC, Chimassorb 2020, 119, 944, Hostavin N30 from Hoechst, Cyasorb UV-3346, UV-3526 from Cytec, Uval 299 from GLC And SanduvorPR-31 manufactured by Clariant.
  • These light stabilizers may be used alone or in combination of two or more.
  • the content is usually 0.005 to 5 parts by mass, preferably 0.01 to 2 parts by mass with respect to 100 parts by mass in total of the components (A), (B) and (C).
  • the composition of the present invention gives a cured product by heat treatment at a temperature higher than the temperature at which radicals are generated from the component (D) (in the case of a photoradical polymerization initiator, by irradiation with light).
  • the curing conditions may be appropriately adopted in consideration of the decomposition characteristics of the initiator. For example, methods such as compression molding, liquid transfer molding, liquid injection molding, and coating can be used in addition to curing by potting. Moreover, the hardening method of the photocurable resin using a UV light source can also be used. You may pre-polymerize the composition of this invention before hardening.
  • a cured product obtained by curing the composition of the present invention is preferably used as a sealing material.
  • sealing material examples include a sealing material for an optical semiconductor and a sealing material for a light receiving element.
  • the element to be sealed include a light emitting diode (LED) chip, a semiconductor laser, a photodiode, a photo interrupter, a photo coupler, A phototransistor, an electroluminescent element, a CCD, a solar cell, and the like can be given.
  • LED light emitting diode
  • Total luminous flux Blue LED light emitting element (B2424DCI0 made by GeneLite) is bonded to the lead frame with a die bond material in a surface mount LED package (KD-V93B95-B made by Kyocera Corporation), and the lead of the light emitting element and the counter electrode
  • the acrylate composition obtained in the example and the comparative example is filled in the reflector of the light emitting device in which the frame is connected with a gold wire (diameter 30 ⁇ m), and nitrogen is flown at 100 ° C. for 2 hours and further at 130 ° C. for 2 hours. And cured in an oven.
  • a MCPD-3700 manufactured by Otsuka Electronics Co., Ltd. the sample was made to emit light by applying 150 mA in an integrating sphere, and the total luminous flux was measured.
  • the light-emitting device is -40 ° C, 5 minutes, room temperature, 30 seconds in a refrigerant, 110 ° C, 5 minutes, room temperature, 30 seconds in a heat medium. After performing the exposure cycle 1000 times, the ratio of the LED which did not light up by electricity supply was confirmed.
  • Example 1 As component (A), hydrogenated polyisoprene acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name SPIDA) 50 parts by mass, as component (B), 1-adamantyl methacrylate (manufactured by Idemitsu Kosan Co., Ltd., adamantate M- 104) 40 parts by mass, (C) component as glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 10 parts by mass, (D) component as 1,1-bis (t-hexylperoxy) cyclohexane 1 part by mass, ( E) As a component, 67 parts by weight of a glass filler (manufactured by Nippon Frit Co., Ltd., CF0093-20C: average particle size 39 ⁇ m), and as an antioxidant, Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd., compound name: 3) , 9-
  • the composition was poured into a cell made by sandwiching a Teflon (registered trademark) spacer having a thickness of 1 mm between two steel plates and an aluminum plate having a thickness of 0.3 mm between the steel plates and the spacers, and was 150 times in an oven. After heating at 0 ° C. for 1 hour, a semi-transparent 1 mm thick plate-like test piece was obtained by cooling to room temperature. Moreover, the test sample for a total luminous flux measurement and a thermal shock test was produced by the method as described in said (2) and (3). The evaluation results of the obtained cured product are shown in Table 1.
  • Example 2 A composition and a cured product were obtained in the same manner as in Example 1 except that spherical silica (manufactured by Admatechs, trade name Admafine SO-E5, average particle size 1.6 ⁇ m) was used as the component (E). It was. The evaluation results of the obtained cured product are shown in Table 1.
  • spherical silica manufactured by Admatechs, trade name Admafine SO-E5, average particle size 1.6 ⁇ m
  • Comparative Example 1 A composition and a cured product were obtained in the same manner as in Example 1 except that the component (E) was not used. The evaluation results of the obtained cured product are shown in Table 1. In the thermal shock test, LED non-lighting occurred with high probability.
  • Comparative Example 2 Implemented except that 3 parts by mass of (F) fumed silica (manufactured by Nippon Aerosil Co., Ltd., trade name AEROSIL R-202, average particle size 0.014 ⁇ m) was used instead of the component (E) used in Example 1.
  • a composition and a cured product were obtained in the same manner as in Example 1.
  • the evaluation results of the obtained cured product are shown in Table 1. Since the content of the silica fine particles used in the component (F) is small, LED unlighting occurred with high probability in the thermal shock test.
  • Comparative Example 3 A composition was prepared in the same manner as in Comparative Example 2 except that 5 parts by mass of the component (F) used in Comparative Example 2 was used. The amount of silica fine particles having a small average particle diameter was increased from that in Comparative Example 2, and the thixo Due to the property, the mixture stopped flowing, and a cured product of the composition could not be obtained. Therefore, it can be seen that the occurrence of defects in the thermal shock test cannot be suppressed even when fumed silica having a particle size of 5 parts by mass or more and 0.014 ⁇ m is used.
  • Comparative Example 4 instead of the component (E) used in Example 1, 10 parts by mass of titanium oxide fine particles (manufactured by Ishihara Sangyo Co., Ltd., trade name Typaque PC-3, average particle size 0.21 ⁇ m) was used as the component (F). Except for the above, a composition and a cured product were obtained in the same manner as in Example 1. The obtained cured product was white and did not transmit any light. The evaluation results are shown in Table 1.
  • a cured product capable of scattering light emitted from an optical semiconductor at the same time without causing a disconnection failure of a gold wire in a thermal shock test while maintaining a conventional level of heat resistance and adhesion is provided.
  • a composition is provided.
  • the composition of the present invention is suitably used as a raw material for sealing materials such as light emitting elements and light receiving elements in optical semiconductor devices.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Sealing Material Composition (AREA)
  • Led Device Packages (AREA)

Abstract

La présente invention porte sur une composition qui comprend (A) un ou plusieurs composés choisis parmi les huiles de silicone modifiées par (méth)acrylate, les (méth)acrylates d'alkyle à longue chaîne et les (méth)acrylate de polyalkylèneglycol, (B) un composé (méth)acrylate comprenant un groupe hydrocarboné alicyclique lié par une liaison ester, (C) de l'acide (méth)acrylique ou un composé (méth)acrylate ayant un groupe polaire, (D) un initiateur de polymérisation radicalaire et (E) de fines particules à base de silice ayant un diamètre moyen de particule de 0,1-500 µm ou des fibres à base de silice ayant un diamètre moyen de fibre et une longueur de fibre de 0,1-500 µm chacun, la teneur du composant (E) étant de 5-500 parties en masse pour 100 parties en masse de la somme des composants (A), (B) et (C). Cette composition est appropriée pour être utilisée comme matière première pour des agents d'encapsulation. La composition donne un objet durci qui, dans un essai de choc thermique, empêche les fils d'or de développer une défaillance par rupture et qui peut diffuser la lumière émise par le semi-conducteur optique, tout en conservant une résistance à la chaleur et une adhérence à des niveaux classiques.
PCT/JP2012/070763 2011-08-19 2012-08-15 Composition à base d'acrylate WO2013027640A1 (fr)

Priority Applications (2)

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CN201280040391.9A CN103732640A (zh) 2011-08-19 2012-08-15 丙烯酸酯系组合物
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Cited By (1)

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JP2015089922A (ja) * 2013-11-06 2015-05-11 出光興産株式会社 反射材用組成物及びこれを用いた光半導体発光装置

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KR20210012514A (ko) * 2019-07-25 2021-02-03 엘지이노텍 주식회사 광학 레진 및 이를 갖는 조명장치
JP7401334B2 (ja) * 2020-02-06 2023-12-19 ハリマ化成株式会社 リリース剤、および、樹脂成形物の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006093672A (ja) * 2004-08-26 2006-04-06 Toshiba Corp 半導体発光装置
JP2006179804A (ja) * 2004-12-24 2006-07-06 Sharp Corp 光半導体素子および電子機器
JP2007281250A (ja) * 2006-04-07 2007-10-25 Toshiba Corp 半導体発光装置
WO2011016356A1 (fr) * 2009-08-04 2011-02-10 出光興産株式会社 Composition d'acrylate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006093672A (ja) * 2004-08-26 2006-04-06 Toshiba Corp 半導体発光装置
JP2006179804A (ja) * 2004-12-24 2006-07-06 Sharp Corp 光半導体素子および電子機器
JP2007281250A (ja) * 2006-04-07 2007-10-25 Toshiba Corp 半導体発光装置
WO2011016356A1 (fr) * 2009-08-04 2011-02-10 出光興産株式会社 Composition d'acrylate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015089922A (ja) * 2013-11-06 2015-05-11 出光興産株式会社 反射材用組成物及びこれを用いた光半導体発光装置

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CN103732640A (zh) 2014-04-16
KR20140051958A (ko) 2014-05-02
TW201329150A (zh) 2013-07-16

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