CN108117721A - transparent epoxy resin composition and optical semiconductor device - Google Patents
transparent epoxy resin composition and optical semiconductor device Download PDFInfo
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- CN108117721A CN108117721A CN201710992489.9A CN201710992489A CN108117721A CN 108117721 A CN108117721 A CN 108117721A CN 201710992489 A CN201710992489 A CN 201710992489A CN 108117721 A CN108117721 A CN 108117721A
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- epoxy resin
- transparent epoxy
- resin composition
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- optical semiconductor
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 67
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000004065 semiconductor Substances 0.000 title claims abstract description 20
- 230000003287 optical effect Effects 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 150000008301 phosphite esters Chemical class 0.000 claims abstract description 22
- 239000004615 ingredient Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 14
- 239000003566 sealing material Substances 0.000 claims abstract description 10
- 239000002530 phenolic antioxidant Substances 0.000 claims description 17
- 238000007789 sealing Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 description 45
- 238000004519 manufacturing process Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 11
- 235000006708 antioxidants Nutrition 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 230000005764 inhibitory process Effects 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 101001014562 Homo sapiens Male-specific lethal 3 homolog Proteins 0.000 description 4
- 102100032515 Male-specific lethal 3 homolog Human genes 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- -1 aliphatic anhydride Chemical class 0.000 description 3
- 239000000549 coloured material Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 2
- 235000010894 Artemisia argyi Nutrition 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 244000030166 artemisia Species 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241000218606 Pinus contorta Species 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004067 bulking agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 235000000673 shore pine Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The subject of the invention is to provide it is a kind of with lead frame, the adhesiveness of component is excellent and the optical semiconductor device of the transparent epoxy resin composition that is inhibited by thermally-induced xanthochromia etc. and the solidfied material for having used as sealing material the transparent epoxy resin composition.A kind of optical semiconductor device of the solution of the present invention there is provided transparent epoxy resin composition and using the transparent epoxy resin composition, also, the transparent epoxy resin composition contains as essential component：Transparent epoxy resin as A ingredients；Anhydride curing agent as B component；Curing accelerator as C ingredients；Compound containing disulfide bond as D ingredients；And the phosphite ester as E ingredients.
Description
Technical field
A kind of transparent epoxy resin combination of and high temperature excellent the present invention relates to solder heat resistance storage excellent heat resistance
Object and the optical semiconductor device that the transparent epoxy resin composition has been used as sealing material.
Background technology
For the composition epoxy resin used as the seal applications of electronic unit, when by its directly in use, because
The change of color easily occurs for xanthochromia caused by heat, therefore, the dark coloured material such as carbon black is usually added, so that resin combination
The xanthochromia of object is difficult to discover.
The transparent resin composition not comprising coloured material, light color system resin combination in, in order to inhibit because of thermal conductivity
The xanthochromia of cause is, it is necessary to add antioxidant.However, what the antioxidant that epoxy resin is widely used as due to versatility height was used
Phenolic antioxidant, it's hard to say its antioxygenic property is perfect, especially, there is the high temperature in electronic unit installation procedure is short
When baking, 260 DEG C of welded and installeds when the defects of generating xanthochromia.
For this reason, it may be necessary to increase the additive amount of antioxidant, still, when increasing the additive amount of antioxidant, do not only result in
The deterioration of mouldability, the reduction of reliability, and the xanthochromia of antioxidant itself easily become to highlight, and light resistance is also deteriorated.
Further, since assembled in electronic unit using the constituent material with various coefficient of thermal expansion, because
The difference of its coefficient of thermal expansion, in the assembling procedure of electronic unit or during welded and installed and then in actual use, in order to
Between the materials will not be peeling-off, the addition bonding imparting agent usually in resin material.
As bonding imparting agent, for improve surface moist bulking agent, for keep bonding low stress agent also have
A degree of effect, but the effect for the bonding imparting agent of chemical adhesive is very high.Therefore, especially in recent years, for
Inhibit corrosion and be coated with when inhibiting to remove in the lead frame of noble metal, being to resin material addition chemical adhesion imparting agent must not
It can lack.Particularly, in the electronic unit sealed by transparent resin composition, when peeling-off, even if not using ultrasound
Ripple detection device etc., naked eyes are also able to confirm that, therefore, further improve its importance.
But the previous formula for only adding phenolic antioxidant does not have the effect for inhibiting to remove, especially be coated with it is expensive
In the lead frame of metal, some is even peeling after molding.
Therefore, as the bonding imparting agent for noble metal, addition containing disulfide bond (S -- S) compound etc. has been inquired into.
Although this contain disulfide bond (S -- S) compound lead to it is too small amount of addition can just improve bonding force, when each packaging part
When noble metal plating area becomes larger, still there is the tendency being peeling.
On the other hand, stripping inhibition can be improved by increasing the additive amount containing disulfide bond (S -- S) compound, but
At the same time, with just cured material also yellowy problem.This xanthochromia is due to containing S -- S combound itself for deeply
Yellow and the phenomenon that occur, when for transparent resin, additive amount cannot be increased to more than specified amount.
In addition, compound containing S -- S can reduce the curability of resin combination often, for this purpose, when increase curing accelerator
When, the reason for being also possible to become xanthochromia.
Prior art literature：
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-40972 publications；
Patent document 2：Japanese Unexamined Patent Publication 2005-17321 publications.
The content of the invention
The present invention was completed to solve the above problem.
Therefore, it is an object of the present invention to provide a kind of excellent with the adhesiveness of lead frame, component, and caused by heat
Xanthochromia etc. is able to the transparent epoxy resin composition inhibited and as sealing material the photosemiconductor of its solidfied material is used to fill
It puts.
The present inventor is careful studied in order to achieve the above objectives, it turns out that, by being added on a small quantity containing two sulphur
Key (S -- S) compound and using phosphite ester, can take into account the performance of high adherence and the inhibition of xanthochromia, complete as a result,
The present invention.
That is, transparent epoxy resin composition of the invention, which is characterized in that contain (A) transparent epoxy as essential component
Resin, (B) anhydride curing agent, (C) curing accelerator, (D) compound containing disulfide bond and (E) phosphite ester.
The optical semiconductor device of the present invention, which is characterized in that it has：The optical semiconductor being disposed on the substrate；With
And the sealing material of above-mentioned optical semiconductor is sealed by the solidfied material of the transparent epoxy resin composition of the present invention.
Transparent epoxy resin composition according to the present invention can obtain the xanthochromia caused by heat and be inhibited, and fast light
The excellent solidfied material of property, especially, is capable of providing the resin combination for the sealing material for being suitable as photosemiconductor.This is transparent
Composition epoxy resin is used as the optical semiconductor device that sealing material obtains, and can effectively inhibit the sealing after its manufacture
It removes, becomes the high device of reliability.
Specific embodiment
As described above, the transparent epoxy resin composition of the present invention is as essential component, comprising (A) transparent epoxy resin,
(B) anhydride curing agent, (C) curing accelerator, (D) contain disulfide bond (S -- S) compound and (E) phosphite ester.In the following, in detail
Illustrate each ingredient for forming the transparent epoxy resin composition of the present invention.
(A) transparent epoxy resin used in the present invention is that at least tool there are two the compound of epoxy group, is in its molecule
The epoxy resin of the solidfied material of the transparency can be obtained after curing.For (A) transparent epoxy resin, as long as with this
Characteristic, to its molecular structure and molecular weight etc. without special restriction, can include extensively makes usually as sealing material
Epoxy resin.As (A) transparent epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy tree can be enumerated
Fat, bisphenol-A epoxy resin, o-cresol phenolic epoxy varnish, polyfunctional epoxy resin, ester ring type asphalt mixtures modified by epoxy resin
Fat, organic-silicon hybridization epoxy resin etc..Wherein, bisphenol f type epoxy resin, the moisture absorption of molded product treated solder heat resistance
It is excellent.Above-mentioned (A) transparent epoxy resin can be used alone and one kind or can also mix two or more uses, can also and its
He is used in combination well known epoxy resin.By and with polyfunctional epoxy resin, solder heat resistance can be improved.
(B) anhydride curing agent used in the present invention is the acid to play a role as the curing agent of (A) transparent epoxy resin
Acid anhydride.As (B) anhydride curing agent, known acid anhydrides can be enumerated, for example, can enumerate ester ring type acid anhydrides, aliphatic anhydride,
Aromatic anhydride etc..Should (B) anhydride curing agent can be used alone and one kind or can also mix two or more uses, can be with
It is used in combination with other well known anhydride curing agents.
(A) mass ratio of transparent epoxy resin and (B) anhydride curing agent is contemplated that respective equivalent and determines that (acid anhydrides is solid
The equivalent of use level/anhydride curing agent of agent)/(equivalent of use level/epoxy resin of epoxy resin) preferably 1.0~
1.2 scope.If more than 1.0, since the transparency of solidfied material is good, briliancy will not be reduced；If less than 1.2, it will not
Glass transition temperature is reduced, curability is good.
(C) curing accelerator used in the present invention is in above-mentioned (A) transparent epoxy resin and (B) anhydride curing agent
The curing accelerator used in curing system.As (C) curing accelerator, known curing accelerator can be enumerated, it is excellent
Select the curing accelerator that impurity concentration is low.As the curing accelerator, cure for example, DBU systems well known to U-CAT etc. can be enumerated
Accelerating agent, imidazoles system curing accelerator, phosphorus system curing accelerator etc..Should (C) curing accelerator can be used alone one kind, Huo Zheye
Two or more uses can be mixed, can also be used in combination with other curing accelerators.
The usage amount for being somebody's turn to do (C) curing accelerator is preferably 0.1~1.0 mass % in resin combination.Promote if curing
The usage rate of agent can then shorten the hardening time of transparent resin composition more than 0.1 mass %.If promote in addition, curing
Into agent usage rate below 1.0 mass %, due to having suitable mobility, fillibility becomes good, even if
Its working life will not be too short under room temperature.
For (D) used in the present invention contains disulfide bond (S -- S) compound, as long as organising containing disulfide bond
Object is closed, and the ratio of the S -- S of the organic compound is preferably 20~40%.In addition, S-S ratios described herein, are
Refer to the quality ratio for the sulphur atom that S -- S is participated in unit formula amount.As (D) containing disulfide bond (S -- S) compound, example
Such as, the compound represented by following chemical formula can be enumerated.
Chemical formula 1：
Chemical formula 2：
Chemical formula 3：
Chemical formula 4：
It is preferred that it is the low and of light color compound of impurity concentration to be somebody's turn to do (D) containing disulfide bond (S -- S) compound.Its match ratio phase
It is 0.01~0.3 mass % for resin combination total amount, is preferably 0.02~0.2 mass %, if the ratio is less than 0.01 matter
% is measured, it is poor to improve the effect of adhesiveness, if more than 0.3 mass %, it is thus not preferred immediately with yellow after curing.
As the compound containing disulfide bond (S -- S), preferably the S -- S ratio of unit formula amount or unit repetitive unit
At least any one compound with intermiscibility in rate height and the epoxy resin and acid anhydrides that are used with the present invention.
For example, the molecular weight of the above-mentioned compound represented by chemical formula 1 is 297, therefore, S -- S ratio is 32 × 2 ÷
297 × 100 ≈ 21.5 are 21.5%.
In addition, the molecular weight of the above-mentioned compound represented by chemical formula 2 is 385, therefore, S -- S ratio is as four
Sulfide calculates, and is 32 × 4 ÷, 385 × 100 ≈ 33.2, is 33.2%.
The ratio of the S -- S is preferably 20~40% or so, if too low, cannot obtain and bond imparting agent as noble metal
Effect；If excessively high, there is the tendency being lower with the intermiscibility of resin component.Wherein, 4,4 '-dithio morpholine, sulfide
The S -- S of coupling agent is easy to the coordination in noble metal face, therefore, is improving adhesiveness and two aspect of intermiscibility to epoxy resin
It is excellent.
(E) phosphite ester used in the present invention, is in the phosphorous acid used as the antioxidant with deoxidation effect
The compound that is substituted by organic group of 3 hydrogen, for example, the compound that alkoxy, phenoxy group etc. have been bonded on phosphorus atoms can be enumerated.
As (E) phosphite ester, such as the compound represented by following chemical formula can be enumerated.
Chemical formula 5：
Chemical formula 6：
Chemical formula 7：
Chemical formula 8：
Chemical formula 9：
As (E) phosphite ester, the preferably low phosphite ester of impurity concentration.(E) phosphite ester can be used alone one kind,
Or two or more uses can be mixed.In addition, the fusing point of (E) phosphite ester is preferably less than 150 DEG C.When the fusing point is more than
At 150 DEG C, decomposition temperature becomes higher, and therefore, has and is difficult to the tendency for showing xanthochromia inhibition.
Being somebody's turn to do (E) phosphite ester has the function of through deoxidation and stabilized radical, but for the imparting of adhesiveness, it should
Deoxidation also functions to important role.Specifically, to when by oxidation surface be in the glued component of inactive state,
The component surface is activated by deoxidation, thereby, it is possible to show the effect of raising bonding force.
In resin combination total amount, the match ratio of (E) phosphite ester is somebody's turn to do as 0.05~3 mass %, is preferably 0.1~2 matter
Measure %.If the match ratio is less than 0.05 mass %, the improvement effect and xanthochromia inhibition of adhesiveness are poor；If more than 3 matter
% is measured, it is thus not preferred since surface bleeding occurring during curing.
(F) phenolic antioxidant used in the present invention, can enumerate the well known phenol system added in resin combination
Antioxidant, preferably fusing point are less than 150 DEG C.Although this is because in order to which (F) antioxidant is made to play a role, antioxidant
Itself have to decompose, if but fusing point it is excessively high, it is impossible to play the reason of its mechanism.
As (F) phenolic antioxidant, preferably its impurity concentration is low, for example, can enumerate what is represented by following chemical formula
Well known phenolic antioxidant compound.
Chemical formula 10：
Chemical formula 11：
Chemical formula 12：
Chemical formula 13：
Chemical formula 14：
Chemical formula 15：
Should (F) phenolic antioxidant can be used alone and one kind or can also mix two or more uses.Moreover, may be used also
To be used in combination with other well known phenolic antioxidants.
The match ratio for being somebody's turn to do (F) phenolic antioxidant is 0.05~3 mass % in resin combination total amount, is preferably 0.1~2
Quality %.When its match ratio is less than 0.05 mass %, the improvement effect and xanthochromia inhibition of adhesiveness are poor；If more than 3 matter
% is measured, then surface bleeding occurs when curing, it is thus not preferred.
The transparent epoxy resin composition of the present invention cures above-mentioned (A) transparent epoxy resin, (B) anhydride curing agent, (C)
Accelerating agent, (D) containing disulfide bond (S -- S) compound and (E) phosphite ester as essential component, but without prejudice to mesh of the present invention
In the range of, addition (F) phenolic antioxidant can also be mated properly into as needed；Such as natural waxes, synthesis wax class
Wait releasing agents；The low stresses imparting agent such as rubber series or silicone-based polymer；The coupling agents such as amine modification and epoxy modified polysiloxane；Dye
The light colors coloured material such as material or pigment；Reactive or non-reacted diluent etc..
It when manufacturing the transparent epoxy resin composition of the present invention, is manufactured when being the sealing material of solid under as room temperature
Known method can be used in method.As this method, for example, can enumerate：Respectively by above-mentioned (A) transparent epoxy resin, (B)
Anhydride curing agent, (C) curing accelerator, (D) are anti-oxidant containing disulfide bond (S -- S) compound, (E) phosphite ester, (F) phenol system
Agent and other compositions cooperation carry out heating melting mixing by roll or kneading etc. and handle, be then allowed to cool and solidify, and
The method for being crushed the transparent epoxy resin composition after curing with appropriate size.According to this method, can be had
There are required characteristic and the sealing material that can be sealed.
The transparent epoxy resin composition of the present invention can be applied to the various electricity such as various electric components or semiconductor element
In the purposes such as coating, insulation, the sealing of subassembly.The curing of the transparent epoxy resin composition can pass through known method
Come carry out.It should be noted that the solidfied material obtained herein is transparent solidfied material." transparent " described in this specification is
Light transmittance is more than 70% shape in arbitrary wave band of the test piece of dinger thickness degree 1mm between 380~780nm of visible wavelength region
State.
In addition, the optical semiconductor device of the present invention is by the way that fixed optical semiconductor on substrate is carried out with above-mentioned material
Sealing, can easily manufacture.As common encapsulating method, transfer molding, injection moulding, compression forming etc. can be enumerated, when
During using the forming method for having used mold and pressure apparatus, carry out vacuum forming as needed, thus, it is possible to improve gap it
Between fillibility, reduce gap.Sealing and solidify afterwards temperature are preferably 150 DEG C or more.
Embodiment
In the following, the present invention is illustrated by embodiment and comparative example, but the present invention is not limited to these embodiments.
In following embodiments and comparative example, " part " refers to " mass parts ".
(embodiment 1)
It, will be as the bisphenol A type epoxy resin (trade name of epoxy resin under normal temperature condition：JER1001, Mitsubishi Chemical
(strain) company manufactures) 41.5 parts and the (trade name of skeletal epoxy resin containing triazine：TEPIC-S, Nissan Chemical Industries (strain) company system
Make) 15.0 parts, anhydride curing agent (trade name：Rikacid TH (リ カ シ ッ De) TH, new Japan Chemical (strain) company manufacture)
40.0 parts, curing accelerator (trade name：UCAT5003, mountain spy (strain) company (サ Application ア プ ロ (strain), San-Apro Ltd.)
Manufacture) 0.4 part, 1 (trade name of compound containing disulfide bond：ACTOR-R, the manufacture of Kawaguchi's chemical industry (strain) company, chemical formula 3 are remembered
The compound of load) 0.1 part, 1 (trade name of phosphite ester：JP-360, the manufacture of north of the city chemical industry (strain) company, chemical formula 5 are recorded
Compound) 0.1 part, 1 (trade name of phenolic antioxidant：BHT, the reagent of Tokyo chemical conversion industry (strain) company manufacture, chemical formula
10 compounds recorded) 0.5 part, hydroxy stearic acid (trade name：KOW, river grind fine chemistry industry and (grind Off ァ イ Application ケ ミ カ Le in river
(strain), Kawaken Fine Chemicals Co., Ltd) manufacture) 2.0 parts mixed, obtain composition epoxy resin.
And then after being kneaded under the conditions of 70~100 DEG C to the composition epoxy resin, it is cooled down, cured and is crushed,
The moulding material of sealing is manufactured.
Using the moulding material manufactured as described above, and pass through transfer molding machine, be heated to 165 DEG C of mold (metal type)
Middle shaping 2 minutes, and then the solidify afterwards when progress 2 is small under the conditions of 150 DEG C, obtain experiment molded product.
(embodiment 2~12, comparative example 1~4)
In addition to using the raw material shown in table 1~3 and content ratio, other are operated similarly to Example 1,
Composition epoxy resin, moulding material and experiment molded product are manufactured respectively in each case.The following institute of raw material as used herein
It states.
(A) ingredient
Bisphenol f type epoxy resin (trade name：JER4004P, the manufacture of Mitsubishi Chemical (strain) company)
(D) ingredient
2 (trade name of compound containing disulfide bond：KBE-846, the manufacture of SHIN-ETSU HANTOTAI's chemical industry (strain) company, chemical formula 4 are recorded
Compound)
(E) ingredient
2 (trade name of phosphite ester：PEP-8, Chinese mugwort Dicon A/S ((strain) ADEKA) manufacture, the chemical combination that chemical formula 7 is recorded
Object)
3 (trade name of phosphite ester：JPP-100, the manufacture of north of the city chemical industry (strain) company, the chemical combination that chemical formula 8 is recorded
Object)
4 (trade name of phosphite ester：JP-650, the manufacture of north of the city chemical industry (strain) company, the chemical combination that chemical formula 9 is recorded
Object)
(F) ingredient
2 (trade name of phenolic antioxidant：IRGANOX 1010, BASF AG (BASF societies) manufacture, chemical formula 14 are remembered
The compound of load)
3 (trade name of phenolic antioxidant：AO-40, Chinese mugwort Dicon A/S ((strain) ADEKA) manufacture, what chemical formula 15 was recorded
Compound)
Other compositions
Hydroxy stearic acid (trade name：KOW, river grind fine chemistry industry and (grind Off ァ イ Application ケ ミ カ Le (strain), Kawaken in river
Fine Chemicals Co., Ltd) manufacture, releasing agent)
DOPO (trade names：EPOCLEAN, the manufacture of three light (strain) company, antioxidant)
(test example)
To light transmittance, bonding force, the solder heat resistance of the experiment molded product that embodiment 1~12 and comparative example 1~4 obtain
Property, briliancy conservation rate, have carried out experiment as described below, its result are summarized and is shown in table 1~3.
Table 1
Table 2
Table 3
(light transmittance)
Under the condition of cure of 165 DEG C × 2 minutes, resin combination is cured, forms the shaping of thickness 1.0mm
Product.By spectrophotometer, (Japanese surface chemistry Co., Ltd. (Jasco) manufactures, trade name：V-570), thickness is determined
Light transmittance under the 460nm wavelength of the molded product of 1.0mm.
In addition, by the molded product of thickness 1.0mm under the conditions of 150 DEG C processing 168 it is small when after, equally determine 460nm
Light transmittance under wavelength.
(bonding force)
In silver-plated frame (size：29mm × 9mm × 0.17mm) on, φ 3.4mm are become using the basal diameter as bonding plane
Mode, resin combination is shaped to trapezoidal or cylindrical, forming temperature at this time is 165 DEG C, molding time is 2 points of kinds,
And determine the shear adhesion power under the conditions of 100 DEG C.
(solder heat resistance)
SOP16 (sizes are molded with the condition of molding of 165 DEG C, 2 minutes：It is 29mm × 9mm × 0.17mm, silver-plated), and 30
DEG C, 70%, 168 it is small when condition (MSL3 conditions) and 60 DEG C, 60%, 120 it is small when condition (MSL2a conditions) under carry out
After moisture absorption processing, the backflow test that maximum temperature is 260 DEG C is implemented.Confirmed using supersonic sounding device and removed, and will stripping
It is more than 50% person as bad counting from area, is obtained [bad encapsulation number/always encapsulate number], and is carried out according to following benchmark
Evaluation.In addition, in Examples 1 to 10, the experiment under the conditions of MLS2a is not carried out.
◎：Without bad encapsulation under the conditions of MSL3 conditions, MSL2a；
○：Without bad encapsulation under the conditions of MSL3；
×：There is bad encapsulation under the conditions of MSL3 conditions, MSL2a.
(briliancy conservation rate)
It is powered to reach to being equipped with blue-led element and having carried out the SOP16 (silver-plated) of wire bonding
120mW, and carried out 500 it is small when light experiment.The light that will be emitted by SOP16 irradiates photoelectricity two from the predetermined distance of 3.5mm
(shore pine photon technology (HamamatsuPhotonics) manufactures pole pipe, trade name：Current value when S1226-8BQ) is as brightness
Degree calculates the briliancy conservation rate since initially by following formula, and is evaluated according to following benchmark.
Conservation rate=(measuring brightness value/initial luminance value) × 100
○：Conservation rate more than 70%；
×：Conservation rate is less than 70%.
The composition epoxy resin of the present invention can inhibit stripping during welded and installed under the conditions of 260 DEG C, moreover, can press down
Xanthochromia caused by being heated for a long time after system installation, and light resistance, inhibition fissility are excellent, are able to confirm that obtain and in the past can not
The significant effect obtained.
From described above, transparent epoxy resin composition of the invention is by and with containing disulfide bond (S -- S) chemical combination
Object, phosphite ester, and then go back and use phenolic antioxidant, it can be obtained with a small amount of additive amount by their multiplication effect
The inhibition of xanthochromia and the solidfied material of excellent in light-resistance caused by heated.It is combined as a result, by the transparent epoxy resin
The optical semiconductor device of object sealing, stripping when becoming assembling and after assembling are able to the high device of the reliability inhibited.
Claims (10)
1. a kind of transparent epoxy resin composition, which is characterized in that it contains as essential component：
Transparent epoxy resin as A ingredients；
Anhydride curing agent as B component；
Curing accelerator as C ingredients；
Compound containing disulfide bond as D ingredients；And
Phosphite ester as E ingredients.
2. transparent epoxy resin composition according to claim 1, wherein,
The ratio of disulfide bond, that is, S -- S of the compound containing disulfide bond as D ingredients is 20~40%.
3. transparent epoxy resin composition according to claim 1 or 2, wherein,
The fusing point of the phosphite ester as E ingredients is less than 150 DEG C.
4. transparent epoxy resin composition described in any one of claim 1 to 3, wherein,
It is also containing the phenolic antioxidant as F ingredients.
5. transparent epoxy resin composition according to claim 4, wherein,
The fusing point of the phenolic antioxidant as F ingredients is less than 150 DEG C.
6. a kind of optical semiconductor device, which is characterized in that it has：
The optical semiconductor being disposed on the substrate；And
Sealing has been carried out to the optical semiconductor by the solidfied material of transparent epoxy resin composition described in claim 1
Sealing material.
7. optical semiconductor device according to claim 6, wherein,
In the transparent epoxy resin composition, the ratio of disulfide bond, that is, S -- S of the compound containing disulfide bond as D ingredients is
20~40%.
8. the optical semiconductor device according to claim 6 or 7, wherein,
In the transparent epoxy resin composition, the fusing point of the phosphite ester as E ingredients is less than 150 DEG C.
9. the optical semiconductor device according to any one of claim 6~8, wherein,
The transparent epoxy resin composition is also containing the phenolic antioxidant as F ingredients.
10. optical semiconductor device according to claim 9, wherein,
The fusing point of the phenolic antioxidant as F ingredients is less than 150 DEG C.
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| JP2016-231257 | 2016-11-29 | ||
| JP2016231257 | 2016-11-29 | ||
| JP2017172880A JP2018090770A (en) | 2016-11-29 | 2017-09-08 | Transparent epoxy resin composition and optical semiconductor device |
| JP2017-172880 | 2017-09-08 |
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| CN108117721A true CN108117721A (en) | 2018-06-05 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113201203A (en) * | 2021-03-15 | 2021-08-03 | 苏州市汇涌进光电有限公司 | Light-cured transparent epoxy material and application thereof |
| CN115651575A (en) * | 2022-09-14 | 2023-01-31 | 江苏科化新材料科技有限公司 | Epoxy resin material and preparation method and application thereof |
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| CN103289317A (en) * | 2013-01-29 | 2013-09-11 | 中科院广州化学有限公司 | LED packaging material, its preparation method and application |
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| CN103289317A (en) * | 2013-01-29 | 2013-09-11 | 中科院广州化学有限公司 | LED packaging material, its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113201203A (en) * | 2021-03-15 | 2021-08-03 | 苏州市汇涌进光电有限公司 | Light-cured transparent epoxy material and application thereof |
| CN115651575A (en) * | 2022-09-14 | 2023-01-31 | 江苏科化新材料科技有限公司 | Epoxy resin material and preparation method and application thereof |
| CN115651575B (en) * | 2022-09-14 | 2024-03-01 | 江苏中科科化新材料股份有限公司 | Epoxy resin material and preparation method and application thereof |
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