WO2018155131A1 - 硬化性オルガノポリシロキサン組成物および半導体装置 - Google Patents
硬化性オルガノポリシロキサン組成物および半導体装置 Download PDFInfo
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- WO2018155131A1 WO2018155131A1 PCT/JP2018/003534 JP2018003534W WO2018155131A1 WO 2018155131 A1 WO2018155131 A1 WO 2018155131A1 JP 2018003534 W JP2018003534 W JP 2018003534W WO 2018155131 A1 WO2018155131 A1 WO 2018155131A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Definitions
- the present invention relates to a curable organopolysiloxane composition and a semiconductor device formed by bonding a semiconductor element with a cured product of the composition.
- a curable organopolysiloxane composition is used for bonding the semiconductor element.
- a curable organopolysiloxane composition for example, in Patent Documents 1 and 2, a substantially linear or cyclic alkenyl group-containing organopolysiloxane, a branched alkenyl group-containing organopolysiloxane, Linear organopolysiloxane having a hydrogen atom bonded to a silicon atom in a molecular chain, branched organopolysiloxane having a silicon atom-bonded hydrogen atom, specifically, an average unit formula: [H (CH 3 ) 2 SiO 1/2 ] 0.67 (SiO 4/2 ) Organopolysiloxane resin represented by 0.33 and average unit formula: [H (CH 3 ) 2 SiO 1/2 ] 0.50 [
- Polysiloxane, branched organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule specifically, average unit formula: [H (CH 3 ) 2 SiO 1/2 ] 0.44
- Organopolysiloxane resin represented by (SiO 4/2 ) 0.56 average unit formula: [H (CH 3 ) 2 SiO 1/2 ] 0.25 [(CH 3 ) 3 SiO 1/2 ] 0.5 25 (SiO 4/2 ) 0.50 organopolysiloxane resin, or average unit formula: [(CH 3 ) 3 SiO 1/2 ] 0.20 [H (CH 3 ) SiO 2/2 ] 0 represented by .40 (SiO 4/2) 0.40
- Organopolysiloxane resins, and curable organopolysiloxane composition consisting of a hydrosilylation reaction catalyst have been proposed.
- the organopolysiloxane resin having silicon-bonded hydrogen atoms is blended in order to adjust the mechanical strength and hardness of the resulting cured product.
- the functional organopolysiloxane composition has a problem that adhesiveness to a semiconductor element is not sufficient, or bubbles are generated in the cured product, resulting in a decrease in adhesive strength.
- An object of the present invention is to provide a curable organopolysiloxane composition that forms a cured product having excellent adhesion to a semiconductor element and few bubbles. Furthermore, another object of the present invention is to provide a semiconductor device having excellent reliability.
- the curable organopolysiloxane composition of the present invention comprises (A) an organopolysiloxane having at least two alkenyl groups in one molecule; (B) Average unit formula: (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 2 SiO 3/2 ) c (SiO 4/2 ) d (In the formula, R 1 is the same or different, and is a monovalent hydrocarbon group or hydrogen atom having no aliphatic unsaturated carbon bond, provided that at least two R 1 in one molecule are hydrogen atoms.
- R 2 is a monovalent hydrocarbon group having no aliphatic unsaturated bond
- a, b, and c are 0 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 0.2, 0, respectively.
- ⁇ D ⁇ 1, provided that 0.6 ⁇ a / d ⁇ 1.5, 1.5 ⁇ b / d ⁇ 3, and a + b + c + d 1.
- the present composition contains (D) 1 to 20 parts by mass of fumed silica having a BET specific surface area of 20 to 200 m 2 / g with respect to a total of 100 parts by mass of the components (A) to (C). It is preferable.
- the present composition preferably contains 0.001 to 5 parts by mass of (E) the hydrosilylation reaction inhibitor with respect to a total of 100 parts by mass of the components (A) to (C).
- the present composition preferably contains 0.01 to 10 parts by mass of (F) an adhesion promoter with respect to 100 parts by mass in total of the components (A) to (C).
- the composition comprises (G) an average formula: R 3 R 4 2 SiO (R 4 2 SiO) m (R 4 HSiO) n SiR 4 2 R 3
- R 3 is the same or different monovalent hydrocarbon group or hydrogen atom having no aliphatic unsaturated carbon bond
- R 4 is the same or different having an aliphatic unsaturated carbon bond.
- No monovalent hydrocarbon group m is a number from 0 to 50
- n is a number from 0 to 50, provided that when n is 0, R 3 is a hydrogen atom.
- Such a composition is preferably cured to form a cured product having a type D durometer hardness of 30 to 70 as defined in JIS K 6253.
- this composition is suitable as an adhesive for semiconductor elements.
- the semiconductor device of the present invention is characterized in that a semiconductor element is bonded by a cured product of the above curable organopolysiloxane composition.
- the curable organopolysiloxane composition of the present invention is characterized by excellent adhesion to semiconductor elements and forming a cured product with few bubbles.
- the semiconductor device of the present invention is characterized by excellent reliability.
- FIG. 1 is a cross-sectional view of a surface mounted light emitting diode (LED) device that is an example of a semiconductor device of the present invention.
- LED surface mounted light emitting diode
- (A) component is an organopolysiloxane having at least two alkenyl groups in one molecule.
- alkenyl group in the component (A) the vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, etc. Twelve alkenyl groups are exemplified, and a vinyl group is preferable.
- Examples of the group bonded to the silicon atom other than the alkenyl group in the component (A) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, Alkyl groups having 1 to 12 carbon atoms such as hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group; carbon such as phenyl group, tolyl group, xylyl group and naphthyl group An aryl group having 6 to 20 carbon atoms; an aralkyl group having 7 to 20 carbon atoms such as a benzyl group, a phenethyl group, and a phenylpropy
- the molecular structure of the component (A) is not particularly limited, and examples thereof include a straight chain, a partially branched straight chain, a branched chain, a ring, or a three-dimensional network structure.
- the component (A) may be a single organopolysiloxane having these molecular structures or a mixture of two or more organopolysiloxanes having these molecular structures.
- Linear, partially branched, or cyclic organopolysiloxanes have an average unit formula: (R 5 3 SiO 1/2 ) e (R 5 2 SiO 2/2 ) f (R 5 SiO 3/2 ) g (SiO 4/2 ) h (HO 1/2 ) i It is represented by
- R 5 is the same or different monovalent hydrocarbon group, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group
- Alkyl groups having 1 to 12 carbon atoms such as a group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group; vinyl group, allyl group, butenyl group, pentenyl group, An alkenyl group having 2 to 12 carbon atoms such as a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group and a dodecenyl group; -20 aryl
- the organopolysiloxane is preferably liquid at 25 ° C., specifically, the viscosity at 25 ° C.
- the viscosity is in the range of 3 to 100,000 mPa ⁇ s, or in the range of 5 to 5,000 mPa ⁇ s. It is preferable that This is because the mechanical strength of the resulting cured product is improved when the viscosity is equal to or higher than the lower limit of the above range. On the other hand, when the viscosity is equal to or lower than the upper limit of the above range, handling workability of the resulting composition is improved. It is because it improves.
- organopolysiloxane examples include organopolysiloxanes represented by the following average unit formula.
- Vi represents a vinyl group
- Me represents a methyl group
- Ph represents a phenyl group.
- organopolysiloxane represented by the following average formula is also illustrated.
- Vi and Me are the same as described above.
- an organopolysiloxane having a branched or three-dimensional network structure has an average unit formula: (R 5 3 SiO 1/2 ) j (R 5 2 SiO 2/2 ) k (R 5 SiO 3/2 ) l (SiO 4/2 ) p (HO 1/2 ) q It is represented by
- R 5 is the same or different monovalent hydrocarbon group, the same groups as those exemplified. However, at least 2 R 5 in one molecule is the alkenyl group, preferably a vinyl group.
- the property at 25 ° C. is not particularly limited, and may be liquid or solid as long as it is compatible with the above-described chain, partially branched linear or cyclic organopolysiloxane.
- an organopolysiloxane represented by the following average composition formula is exemplified.
- Vi, Me, and Ph are the same as described above.
- ViMePhSiO 1/2 ) 0.10 (Me 3 SiO 1/2 ) 0.45 (SiO 4/2 ) 0.45 (HO 1/2 ) 0.03
- Component (A) is composed of 15 to 100% by mass of the above-mentioned linear, partially branched or cyclic organopolysiloxane, and the branched or three-dimensional network structure organopolysiloxane of 0 to 85% by weight. % Is preferable. This is because when the content of the former organopolysiloxane is not less than the lower limit of the above range, sufficient flexibility can be imparted to the resulting cured product.
- Such component (A) is preferably liquid at 25 ° C. because it has good handling workability.
- the viscosity at 25 ° C. is in the range of 100 to 5,000,000 mPa ⁇ s. Or within a range of 500 to 100,000 mPa ⁇ s.
- Component (B) is an average unit formula: (R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 2 SiO 3/2 ) c (SiO 4/2 ) d It is the organopolysiloxane resin represented by these.
- R 1 is the same or different, a monovalent hydrocarbon group or a hydrogen atom having no aliphatic unsaturated carbon bond.
- the monovalent hydrocarbon group for R 1 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group.
- Alkyl groups having 1 to 12 carbon atoms such as a group, nonyl group, decyl group, undecyl group, dodecyl group; aryl groups having 6 to 20 carbon atoms, such as phenyl group, tolyl group, xylyl group, naphthyl group; Aralkyl groups having 7 to 20 carbon atoms such as benzyl group, phenethyl group and phenylpropyl group; groups in which part or all of hydrogen atoms of these groups are substituted with halogen atoms such as fluorine atom, chlorine atom or bromine atom Is exemplified. However, at least 2 R 1 in one molecule is a hydrogen atom.
- R 2 is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and examples thereof include the same groups as R 1 .
- the weight average molecular weight (Mw) of the component (B) is preferably 6,000 or more, 8,000 or more, and more preferably 10,000 or more. This is because when the weight average molecular weight of the component (B) is not less than the above lower limit, the adhesive strength of the obtained cured product is good, and the generation of bubbles in the cured product is suppressed.
- the content of the component (B) is such that the silicon-bonded hydrogen atoms in the component (B) are in the range of 0.5 to 5 moles with respect to a total of 1 mole of alkenyl groups in the component (A).
- the amount is preferably in the range of 0.5 to 3 mol, or in the range of 0.5 to 2 mol. Is the amount.
- Component (C) is a hydrosilylation reaction catalyst for accelerating the hydrosilylation reaction of the composition.
- a component (C) is preferably a platinum group element catalyst or a platinum group element compound catalyst, such as a platinum-based catalyst, a rhodium-based catalyst, or a palladium-based catalyst, and preferably a platinum-based catalyst.
- Platinum-based catalysts include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and diolefin complexes, platinum-olefin complexes, platinum bis (acetoacetate), platinum bis (acetyl) Platinum-carbonyl complexes such as acetonate), chloroplatinic acid / divinyltetramethyldisiloxane complexes, chloroplatinic acid / alkenylsiloxane complexes such as chloroplatinic acid / tetravinyltetramethylcyclotetrasiloxane complexes, platinum / divinyltetramethyldisiloxane Complexes, platinum / alkenylsiloxane complexes such as platinum / tetravinyltetramethylcyclotetrasiloxane complexes, and complexes of chloroplatinic acid and acetylene alcohols are exe
- alkenylsiloxane examples include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxane oligomers in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxane oligomers in which the vinyl groups of these alanyl siloxanes are substituted with allyl groups, hexenyl groups, and the like.
- 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the resulting platinum-alkenylsiloxane complex has good stability.
- platinum-alkenylsiloxane complexes are converted to 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 1,3-diallyl-1 1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane It is preferably dissolved in an alkenylsiloxane oligomer such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane or an organosiloxane oligomer such as dimethylsiloxane oligomer. It is preferably dissolved in the alkenylsiloxane oligomer.
- the content of the component (C) is not limited as long as it is an amount that promotes the curing of the composition.
- the platinum group metal atom in the component particularly a platinum atom, with respect to the composition. Is preferably in an amount in the range of 0.01 to 500 ppm, an amount in the range of 0.01 to 100 ppm, or an amount in the range of 0.1 to 50 ppm.
- the content of the component (C) is at least the lower limit of the above range, the resulting composition has good curability, and when it is below the upper limit of the above range, the resulting cured product is colored, etc. This is because it becomes difficult to cause this problem.
- the composition preferably contains (D) fumed silica having a BET specific surface area of 20 to 200 m 2 / g for the purpose of improving handling workability and adhesiveness.
- the content of the component (D) is not limited, but since the mechanical properties of the resulting cured product are good, 1 to 20 parts by mass with respect to 100 parts by mass in total of the components (A) to (C). It is preferable to be within the range.
- the composition preferably contains (E) a hydrosilylation reaction inhibitor in order to extend the pot life at room temperature and improve the storage stability.
- E 1-ethynylcyclohexane-1-ol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyne- Alkyne alcohols such as 2-ol; Enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1 Methylalkenylsiloxane oligomers such as 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane; dimethylbis (3-methyl Alkynooxysilanes such as -1-butyne-3-oxy) silane
- the content of the component (E) is not limited, and is an amount sufficient to suppress gelation or curing during mixing of the component (A), the component (B), and the component (C), and is sufficient for the present composition. Since the pot life is given, it is within the range of 0.0001 to 5 parts by mass, within the range of 0.01 to 5 parts by mass, or 0 with respect to 100 parts by mass in total of the components (A) to (C). It is preferably in the range of 0.01 to 3 parts by mass.
- the composition preferably contains (F) an adhesion promoter in order to further improve the adhesion to the substrate that is in contact with the curing process.
- adhesion promoter known ones that can be added to a curable organopolysiloxane composition that cures by a hydrosilylation reaction can be used.
- trialkoxysiloxy group for example, trimethoxysiloxy group, triethoxysiloxy group
- trialkoxysilylalkyl group for example, trimethoxysilylethyl group, triethoxysilylethyl group
- Organosilane having hydrosilyl group or alkenyl group for example, vinyl group, allyl group
- trialkoxysiloxy group or trisilane An organosilane having an alkoxysilylalkyl group and a methacryloxyalkyl group (for example, 3-methacryloxypropyl group), or an organosiloxane oligomer having a linear structure, a branched structure or a cyclic structure having about 4 to 20 silicon atoms;
- the content of the component (F) is not limited, but it does not promote curing characteristics or discoloration of the cured product. Therefore, the content of component (A) to component (C) is 0.01 to It is preferably in the range of 10 parts by mass or in the range of 0.01 to 5 parts by mass.
- organopolysiloxane which has a silicon atom bond hydrogen atom other than the said (B) component as needed.
- the organopolysiloxane represented by these is illustrated.
- R 3 is the same or different monovalent hydrocarbon group or hydrogen atom having no aliphatic unsaturated carbon bond.
- Examples of the monovalent hydrocarbon group for R 3 include the same monovalent hydrocarbon groups as those for R 1 .
- R 4 is the same or different monovalent hydrocarbon group having no aliphatic unsaturated carbon bond, and the same monovalent hydrocarbon group as R 1 is exemplified.
- n is a number from 0 to 50, provided that when n is 0, R 3 is a hydrogen atom.
- organopolysiloxane examples include organopolysiloxanes having the following average structural formula.
- Me and Ph are the same as described above.
- the silicon-bonded hydrogen atom in the component (G) is (A)
- the amount is preferably 0.5 mol at most, or 0.3 mol at most with respect to 1 mol of the total of alkenyl groups in the component.
- the present composition includes, as other optional components, inorganic fillers such as silica, glass, alumina and zinc oxide other than the component (D); silicone rubber powder; silicone resin, polymethacrylate Resin powder such as resin; heat-resistant agent, dye, pigment, flame retardant, solvent and the like may be blended.
- inorganic fillers such as silica, glass, alumina and zinc oxide other than the component (D)
- silicone rubber powder silicone resin, polymethacrylate Resin powder such as resin
- heat-resistant agent, dye, pigment, flame retardant, solvent and the like may be blended.
- the composition is preferably liquid at 25 ° C. from the viewpoint of handling workability, and the viscosity at 25 ° C. is preferably in the range of 10 to 1,000,000 mPa ⁇ s.
- the viscosity at 25 ° C. is preferably in the range of 1,000 to 500,000 mPa ⁇ s.
- the composition is cured by standing at room temperature or by heating, but it is preferably heated for rapid curing.
- the heating temperature is preferably in the range of 50 to 200 ° C.
- Such a composition includes a metal such as steel, stainless steel, aluminum, copper, silver, titanium, and a titanium alloy; a semiconductor element such as a silicon semiconductor, a gallium phosphide semiconductor, a gallium arsenide semiconductor, and a gallium nitride semiconductor; Excellent initial adhesion and adhesion durability to ceramic, glass, thermosetting resin, thermoplastic resin having a polar group, etc., especially adhesion durability when subjected to a cooling / heating cycle.
- a metal such as steel, stainless steel, aluminum, copper, silver, titanium, and a titanium alloy
- a semiconductor element such as a silicon semiconductor, a gallium phosphide semiconductor, a gallium arsenide semiconductor, and a gallium nitride semiconductor
- This composition is preferably cured to form a cured product having a type D durometer hardness of 30 to 70 as defined in JIS K 6253. This is because if the hardness is less than the lower limit of the above range, the cohesive force is poor and sufficient strength and adhesiveness can not be obtained, while if the upper limit of the above range is exceeded, the cured product becomes brittle, This is because sufficient adhesiveness cannot be obtained.
- the semiconductor device of the present invention is characterized in that the semiconductor element in the housing is bonded by a cured product of an adhesive made of the above composition.
- the semiconductor element include a light emitting diode (LED), a semiconductor laser, a photodiode, a phototransistor, a solid-state imaging, a photocoupler light emitter and a light receiver, and particularly a light emitting diode (LED). It is preferable.
- the substrate on which the optical semiconductor element is mounted is no exception.
- This substrate includes conductive metals such as silver, gold and copper; non-conductive metals such as aluminum and nickel; thermoplastic resins mixed with white pigments such as PPA and LCP; epoxy resins, BT resins, polyimide resins, Examples thereof include thermosetting resins containing white pigments such as silicone resins; ceramics such as alumina and alumina nitride. Since this composition has favorable adhesiveness with respect to an optical semiconductor element and a board
- FIG. 1 is a cross-sectional view of a single surface-mounted light emitting diode (LED) device, which is a typical example of a semiconductor device.
- LED light emitting diode
- a light emitting diode (LED) chip 5 is bonded to a die pad 3 in a polyphthalamide (PPA) resin casing 1 by an adhesive 4.
- PPA polyphthalamide
- 5 and the inner lead 2 are wire-bonded by a bonding wire 6 and sealed together with an inner wall of the housing by a sealing material 7.
- the curable organopolysiloxane composition of the present invention is used as a composition for forming the adhesive 4.
- the viscosity in an Example and a comparative example is a value in 25 degreeC
- Vi represents a vinyl group
- Me represents a methyl group
- the ratio of SiH / Vi is the ratio of component (b-1) to component (b-6) with respect to a total of 1 mol of vinyl groups of component (a-1) to component (a-7) in the composition.
- the value represents the total number of moles of silicon-bonded hydrogen atoms of the component.
- Component 1-ethynylcyclohexane-1-ol
- Component Condensation reaction product of methyl vinyl siloxane oligomer with blocked silanol groups at both ends of a molecular chain having a viscosity of 30 mPa ⁇ s at 25 ° C. and 3-glycidoxypropyltrimethoxysilane
- the hardness, die shear strength, and the number of bubbles in the cured products obtained by curing the curable organopolysiloxane compositions in the examples and comparative examples were measured as follows.
- a sheet-like cured product was produced by press-molding the curable organopolysiloxane composition at 150 ° C. for 1 hour. The hardness of the sheet-like cured product was measured with a type D durometer defined in JIS K 6253.
- the curable organopolysiloxane composition of the present invention is useful as an adhesive for semiconductor elements such as light emitting diodes (LEDs), semiconductor lasers, photodiodes, phototransistors, solid-state imaging, and light emitters and photoreceptors for photocouplers. Further, since the semiconductor device of the present invention has excellent reliability, it is useful as an optical semiconductor device such as an optical device, an optical device, a lighting device, and a lighting device.
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Abstract
Description
(A)一分子中に少なくとも2個のアルケニル基を有するオルガノポリシロキサン、
(B)平均単位式:
(R1 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d
(式中、R1は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基もしくは水素原子であり、但し、一分子中、少なくとも2個のR1は水素原子であり、R2は脂肪族不飽和結合を有さない一価炭化水素基であり、a、b、cはそれぞれ、0<a<1、0<b<1、0≦c<0.2、0<d<1、但し、0.6≦a/d≦1.5、1.5≦b/d≦3、かつa+b+c+d=1を満たす数である。)
で表されるオルガノポリシロキサンレジン{(A)成分中のアルケニル基に対する(B)成分中のケイ素原子結合水素原子のモル比が0.5~5となる量}、
および
(C)ヒドロシリル化反応用触媒(本組成物を硬化させるのに十分な量)
から少なくともなる。
R3R4 2SiO(R4 2SiO)m(R4HSiO)nSiR4 2R3
(式中、R3は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基もしくは水素原子であり、R4は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基であり、mは0~50の数、nは0~50の数であり、但し、nが0であるとき、R3は水素原子である。)
で表されるオルガノポリシロキサンを、(A)成分中のアルケニル基に対して(G)成分中のケイ素原子結合水素原子のモル比が多くとも0.3となる量含有してもよい。
(R5 3SiO1/2)e(R5 2SiO2/2)f(R5SiO3/2)g(SiO4/2)h(HO1/2)i
で表される。
(ViMe2SiO1/2)0.012(Me2SiO2/2)0.988
(ViMe2SiO1/2)0.007(Me2SiO2/2)0.993
(Me3SiO1/2)0.007(Me2SiO2/2)0.983(MeViSiO2/2)0.010
(Me3SiO1/2)0.01(MeViSiO1/2)0.01(Me2SiO2/2)0.96(MeSiO3/2)0.02
(ViMe2SiO1/2)0.005(Me2SiO2/2)0.895(MePhSiO2/2)0.100
(MeViSiO2/2)3
(MeViSiO2/2)4
(MeViSiO2/2)5
(R5 3SiO1/2)j(R5 2SiO2/2)k(R5SiO3/2)l(SiO4/2)p(HO1/2)q
で表される。
(ViMe2SiO1/2)0.10(Me3SiO1/2)0.33(SiO4/2)0.57(HO1/2)0.03
(ViMe2SiO1/2)0.13(Me3SiO1/2)0.35(SiO4/2)0.52(HO1/2)0.02
(ViMePhSiO1/2)0.10(Me3SiO1/2)0.45(SiO4/2)0.45(HO1/2)0.03
(ViMe2SiO1/2)0.09(Me3SiO1/2)0.31(SiO4/2)0.60(HO1/2)0.04
(ViMe2SiO1/2)0.10(Me3SiO1/2)0.40(SiO4/2)0.50(HO1/2)0.03
(R1 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d
で表されるオルガノポリシロキサンレジンである。
(Me3SiO1/2)0.23(MeHSiO2/2)0.51(SiO4/2)0.26
で表されるオルガノポリシロキサン、平均単位式:
(Me3SiO1/2)0.24(MeHSiO2/2)0.49(SiO4/2)0.27
で表されるオルガノポリシロキサン、平均単位式:
(Me3SiO1/2)0.24(Me2SiO2/2)0.10(MeHSiO2/2)0.40(SiO4/2)0.26
で表されるオルガノポリシロキサンが例示される。
R3R4 2SiO(R4 2SiO)m(R4HSiO)nSiR4 2R3
で表されるオルガノポリシロキサンが例示される。
Me3SiO(MeHSiO)10SiMe3
HMe2SiO(Me2SiO)10SiMe2H
Me3SiO(MeHSiO)80SiMe3
Me3SiO(Me2SiO)30(MeHSiO)30SiMe3
Me2PhSiO(MeHSiO)35SiMe2Ph
本発明の半導体装置は、筺体内の半導体素子が上記組成物からなる接着剤の硬化物により接着されていることを特徴とする。この半導体素子としては、具体的には、発光ダイオード(LED)、半導体レーザ、フォトダイオード、フォトトランジスタ、固体撮像、フォトカプラー用発光体と受光体が例示され、特に、発光ダイオード(LED)であることが好ましい。
(Me2ViSiO1/2)0.042(Me2SiO2/2)0.958
で表される、粘度60mPa・sのオルガノポリシロキサン(ビニル基の含有量=1.53質量%)
(a-2)成分:平均単位式:
(Me2ViSiO1/2)0.012(Me2SiO2/2)0.988
で表される、粘度550mPa・sのオルガノポリシロキサン(ビニル基の含有量=0.45質量%)
(a-3)成分:平均式:
(MeViSiO)4
で表される、粘度4mPa・sの環状メチルビニルポリシロキサン(ビニル基の含有量=30質量%)
(a-4)成分:平均式:
HO(MeViSiO)20H
で表される、粘度30mPa・sのメチルビニルポリシロキサン(ビニル基の含有量=30質量%)
(a-5)成分:平均単位式:
(Me2ViSiO1/2)0.55(Me3SiO1/2)0.05(SiO4/2)0.40
で表される、室温で固体のオルガノポリシロキサン(ビニル基の含有量=19.0質量%)
(a-6)成分:平均単位式:
(Me2ViSiO1/2)0.09(Me3SiO1/2)0.43(SiO4/2)0.48(HO1/2)0.03
で表される、室温で固体のオルガノポリシロキサン(ビニル基の含有量=3.0質量%)
(a-7)成分:平均単位式:
(Me2ViSiO1/2)0.10(Me3SiO1/2)0.45(SiO4/2)0.45(HO1/2)0.02
で表される、室温で固体のオルガノポリシロキサン(ビニル基の含有量=3.0質量%)
(Me3SiO1/2)0.23(MeHSiO2/2)0.51(SiO4/2)0.26
で表されるオルガノポリシロサキン(重量平均分子量=18000、ケイ素原子結合水素原子の含有量=0.78質量%)
(b-2)成分:粘度が510mPa・sであり、平均単位式:
(Me3SiO1/2)0.24(MeHSiO2/2)0.49(SiO4/2)0.27
で表されるオルガノポリシロサキン(重量平均分子量=16300、ケイ素原子結合水素原子の含有量=0.75質量%)
(b-3)成分:粘度が640mPa・sであり、平均単位式:
(Me3SiO1/2)0.24(Me2SiO2/2)0.10(MeHSiO2/2)0.40(SiO4/2)0.26
で表されるオルガノポリシロサキン(重量平均分子量=15400、ケイ素原子結合水素原子の含有量=0.78質量%)
(b-4)成分:粘度が230mPa・sであり、平均単位式:
(HMe2SiO1/2)0.51(Me2SiO2/2)0.15(SiO4/2)0.34(HO1/2)0.03
で表されるオルガノポリシロサキン(重量平均分子量=2100、ケイ素原子結合水素原子の含有量=0.80質量%)
(b-5)成分:粘度が120mPa・sであり、平均単位式:
(HMe2SiO1/2)0.67(SiO4/2)0.33
で表されるオルガノポリシロキサン(重量平均分子量=1310、ケイ素原子結合水素原子の含有量=0.95質量%)
(b-6)成分:粘度が10mPa・sであり、平均式:
Me3SiO(MeHSiO)10SiMe3
で表されるオルガノポリシロキサン(重量平均分子量=8800、ケイ素原子結合水素原子の含有量=1.6質量%)
(d)成分:BET比表面積が115~165m2/gであり、その表面がヘキサメチルジシラザンで疎水化処理されたフュームドシリカ(日本アエロジル社製の商品名:RX200)
(e)成分:1-エチニルシクロヘキサン-1-オール
(f)成分:25℃における粘度が30mPa・sである分子鎖両末端シラノール基封鎖メチルビニルシロキサンオリゴマーと3-グリシドキシプロピルトリメトキシシランの縮合反応物
硬化性オルガノポリシロキサン組成物を150℃で1時間プレス成形することによりシート状硬化物を作製した。このシート状硬化物の硬さをJIS K 6253に規定されるタイプDデュロメータにより測定した。
25mm×75mmの銀めっきした鋼板上に、硬化性オルガノポリシロキサン組成物をディスペンサーにより約300mgづつを5ヶ所に塗布した。次に、この組成物に厚さ1mmの10mm角のガラス製チップを被せ、1kgの板により圧着した状態で、150℃で2時間加熱して硬化させた。その後、室温に冷却し、シェア強度測定装置(西進商事株式会社製のボンドテスターSS-100KP)によりダイシェア強度を測定した。
前記方法により作製したダイシェア試験片内の気泡の数を目視により数えた。
表1に示した混合比で硬化性オルガノポリシロキサン組成物を調製した。硬化物の諸特性を上記のようにして測定し、それらの結果を表1に示した。
2 インナーリード
3 ダイパッド
4 接着材
5 発光ダイオード(LED)チップ
6 ボンディングワイヤ
7 封止材
Claims (8)
- (A)一分子中に少なくとも2個のアルケニル基を有するオルガノポリシロキサン、
(B)平均単位式:
(R1 3SiO1/2)a(R1 2SiO2/2)b(R2SiO3/2)c(SiO4/2)d
(式中、R1は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基もしくは水素原子であり、但し、一分子中、少なくとも2個のR1は水素原子であり、R2は脂肪族不飽和結合を有さない一価炭化水素基であり、a、b、cはそれぞれ、0<a<1、0<b<1、0≦c<0.2、0<d<1、但し、0.6≦a/d≦1.5、1.5≦b/d≦3、かつa+b+c+d=1を満たす数である。)
で表されるオルガノポリシロキサンレジン{(A)成分中のアルケニル基に対する(B)成分中のケイ素原子結合水素原子のモル比が0.5~5となる量}、
および
(C)ヒドロシリル化反応用触媒(本組成物を硬化させるのに十分な量)
から少なくともなる硬化性オルガノポリシロキサン組成物。 - さらに、(D)BET比表面積が20~200m2/gであるフュームドシリカを、(A)~(C)成分の合計100質量部に対して1~20質量部含有する、請求項1に記載の硬化性オルガノポリシロキサン組成物。
- さらに、(E)ヒドロシリル化反応抑制剤を、(A)~(C)成分の合計100質量部に対して0.001~5質量部含有する、請求項1または請求項2に記載の硬化性オルガノポリシロキサン組成物。
- さらに、(F)接着促進剤を、(A)~(C)成分の合計100質量部に対して0.01~10質量部含有する、請求項1乃至3のいずれか1項に記載の硬化性オルガノポリシロキサン組成物。
- さらに、(G)平均式:
R3R4 2SiO(R4 2SiO)m(R4HSiO)nSiR4 2R3
(式中、R3は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基もしくは水素原子であり、R4は同じか又は異なる、脂肪族不飽和炭素結合を有さない一価炭化水素基であり、mは0~50の数、nは0~50の数であり、但し、nが0であるとき、R3は水素原子である。)
で表されるオルガノポリシロキサンを、(A)成分中のアルケニル基に対して(G)成分中のケイ素原子結合水素原子のモル比が多くとも0.5となる量含有する、請求項1乃至4のいずれか1項に記載の硬化性オルガノポリシロキサン組成物。 - 硬化して、JIS K 6253に規定されるタイプDデュロメータ硬さが30~70である硬化物を形成する、請求項1乃至5のいずれか1項に記載の硬化性オルガノポリシロキサン組成物。
- 半導体素子の接着剤である、請求項1乃至6のいずれか1項に記載の硬化性オルガノポリシロキサン組成物。
- 半導体素子が請求項1乃至6のいずれか1項に記載の硬化性オルガノポリシロキサン組成物の硬化物により接着されていることを特徴とする半導体装置。
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WO2021118837A1 (en) * | 2019-12-11 | 2021-06-17 | Dow Silicones Corporation | Rapid hydrosilylation cure composition |
WO2024135805A1 (ja) * | 2022-12-23 | 2024-06-27 | ダウ・東レ株式会社 | 硬化性シリコーン組成物、その硬化生成物、及び前記組成物の使用 |
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JP7475135B2 (ja) * | 2019-12-25 | 2024-04-26 | デュポン・東レ・スペシャルティ・マテリアル株式会社 | 硬化性白色シリコーン組成物、光半導体装置用反射材、および光半導体装置 |
CN114058326B (zh) * | 2021-11-22 | 2023-05-23 | 烟台德邦科技股份有限公司 | 一种粘接及可靠性优异的有机聚硅氧烷组合物及其制备方法 |
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US10927278B2 (en) | 2021-02-23 |
TWI767988B (zh) | 2022-06-21 |
CN110382625A (zh) | 2019-10-25 |
JPWO2018155131A1 (ja) | 2019-11-21 |
KR102226981B1 (ko) | 2021-03-15 |
EP3587498A4 (en) | 2020-12-16 |
EP3587498B1 (en) | 2022-02-16 |
JP6884458B2 (ja) | 2021-06-09 |
KR20190103457A (ko) | 2019-09-04 |
US20190375969A1 (en) | 2019-12-12 |
MY187866A (en) | 2021-10-26 |
TW201842137A (zh) | 2018-12-01 |
EP3587498A1 (en) | 2020-01-01 |
CN110382625B (zh) | 2022-02-18 |
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