CN102408544B - Luminous reflectance hot curing resin composition, the optical semiconductor board for mounting electronic using said composition and optical semiconductor device thereof - Google Patents

Abstract

It is an object of the invention to provide the visible ray after resin solidification high to the reflectance in UV light region, heat-resistant aging or tablet mouldability are superior, and are difficult to when transfer modling produce the luminous reflectance hot curing resin composition of flash and manufacture method thereof and employ optical semiconductor board for mounting electronic and the optical semiconductor device of this resin combination.Described luminous reflectance hot curing resin composition is the luminous reflectance hot curing resin composition containing Thermocurable composition and Chinese white, it is characterized in that, under conditions of molding temperature 100 DEG C～200 DEG C, below moulding pressure 20MPa and molding cycle 60～120 seconds, a length of below the 5mm of flash produced during transfer modling, the luminous reflectance under 350nm～800nm of the wavelength after heat cure is more than 80%.Prepare described luminous reflectance hot curing resin composition, use resin combination, constitute optical semiconductor board for mounting electronic and optical semiconductor device.

Description

Luminous reflectance hot curing resin composition, the optical semiconductor of use said composition Board for mounting electronic and optical semiconductor device thereof

The application is the divisional application of 200780042463.2 (international application no: PCT/JP2007/072069), original application Filing date on November 14th, 2007, the invention entitled luminous reflectance hot curing resin composition of original application and manufacture thereof Method and employ optical semiconductor board for mounting electronic and the optical semiconductor device of described resin combination.

Technical field

The present invention relates in the optical semiconductor device being combined with optical semiconductor and fluorophor equiwavelength's shifter The luminous reflectance hot curing resin composition and the manufacture method thereof that use and employ the photosemiconductor of described resin combination Element mounting substrate and optical semiconductor device.

Background technology

It is combined with LED (Light Emitting Diode: light emitting diode) etc. and is combined with optical semiconductor and fluorescence The optical semiconductor device of body is due to the advantage such as energy-efficient and long-life, it is adaptable to outdoor use equipment, portable liquid crystal backlight The various uses such as lamp and vehicle-mounted purposes, it needs to expand.Being accompanied by this, the high brightness of LED device is improving, element The aging of element material that the increase of rising or direct light energy that thermal discharge increases the set temperature caused causes is considered Problem, in recent years, the opening having indefatigable element material to heat ageing and photoaging becomes problem.In Japanese Laid-Open 2006-140207 publication discloses the optical semiconductor board for mounting electronic that the reflective character after heat resistant test is superior.

But, using the luminous reflectance hot curing resin composition disclosed in above-mentioned publication, utilizing transfer modling system In the case of making substrate, when molding, resin combination oozes out in the gap of the upper die and lower die of molding die, is in easily There is the tendency that resin is dirty.When heating molding, in the case of occurring resin dirty, dirty the highlighting of resin is partly being led as light Body member carries the peristome (recess) of the substrate in region, becomes fault when carrying optical semiconductor.Even if it addition, opening Oral area can carry optical semiconductor, and resin is dirty also becomes the known methods such as utilization lead-in wire joint, and electrical connection light is partly led Fault when body member and metal wiring.That is, resin dirty due to reduce so-called element mounting and lead-in wire engage partly lead Workability when body member manufactures, the most preferred.When semiconductor element manufactures, in order to not cause above-mentioned fault, at substrate Peristome there are resin dirty in the case of, generally, in the manufacturing process of optical semiconductor board for mounting electronic add The removal step that resin is dirty.But, such removal step becomes the loss of cost or manufacturing time, therefore, it is desirable to improve.

Summary of the invention

The present invention makes in view of above-mentioned, the reflectance in the visible ray after its offer resin solidification to UV light region Height, and the luminous reflectance hot curing resin composition occurring resin dirty it is difficult to when transfer modling.It addition, the present invention carries For above-mentioned resin combination, thus the zygosity that goes between is superior, and photoaging and heat ageing are had the solidification of indefatigable phenol system Agent board for mounting electronic and optical semiconductor device.And then, the present invention is provided to efficiency and manufacture above-mentioned optical semiconductor well Board for mounting electronic and the manufacture method of optical semiconductor device.

That is, the present invention is characterized with the item described in following (1)～(26).

(1) a kind of luminous reflectance hot curing resin composition, it is characterised in that its be containing Thermocurable composition and (E) the Thermocurable light of Chinese white is anticaustic penetrates resin combination,

Under conditions of molding temperature 100 DEG C～200 DEG C, below moulding pressure 20MPa and molding cycle 60～120 seconds, The flash length (バ リ さ) produced during transfer modling is below 5mm,

The luminous reflectance under wavelength 350nm～800nm after heat cure is more than 80%.

(2) according to the luminous reflectance hot curing resin composition described in above-mentioned (1), it is characterised in that

Described Thermocurable composition contains (A) epoxy resin.

(3) according to the luminous reflectance hot curing resin composition described in above-mentioned (2), it is characterised in that

Described (A) epoxy resin obtains by mediating (A ') epoxy resin and (B ') firming agent, and containing Viscosity at 100～150 DEG C is at (G) oligomer of 100～2500mPa s scopes.

(4) according to the luminous reflectance hot curing resin composition described in above-mentioned (3), it is characterised in that

Described Thermocurable composition is possibly together with (B) firming agent used along with described (A) epoxy resin, wherein, described (A) match ratio of epoxy resin and described (B) firming agent is: relative to epoxy radicals 1 equivalent in described (A) epoxy resin, energy Active group enough and in described (B) firming agent of this epoxy reaction becomes the ratio of 0.5～0.7 equivalent.

(5) according to the luminous reflectance hot curing resin composition described in above-mentioned (4), it is characterised in that

Described (B) firming agent contains: have the compound of cyamelide skeleton.

(6) according to the luminous reflectance hot curing resin composition described in above-mentioned (5), it is characterised in that

Described (B) firming agent possibly together with: there is the anhydride of the fusing point of more than 35 DEG C.

(7) according to the luminous reflectance hot curing resin composition described in above-mentioned (4), it is characterised in that

Described (B) firming agent contains: cyclohexanetricarboxylic acid's acid anhydride.

(8) according to the luminous reflectance hot curing resin composition described in above-mentioned (7), it is characterised in that

Described cyclohexanetricarboxylic acid's acid anhydride is the compound represented by following structural formula (I).

[changing 1]

(9) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (1)～(8), its feature exists In,

Possibly together with (H) thickening agent, the nanoparticulate fillers that medium particle diameter is 1nm～1000nm should be contained by (H) thickening agent.

(10) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (1)～(8), its feature exists In,

Possibly together with (D) inorganic filling material, Porous filler should be contained or there is oil absorption by (D) inorganic filling material Compound.

(11) according to the luminous reflectance hot curing resin composition described in above-mentioned (10), it is characterised in that

Described Porous filler or have oil absorption compound be shaped as select free spherical shape, broken shape, disk Shape, at least one of group of composition bar-shaped, fibrous.

(12) according to the luminous reflectance hot curing resin composition described in above-mentioned (10) or (11), it is characterised in that

The surface of described Porous filler or the compound with oil absorption has been carried out hydrophobization and has been processed or hydrophiling Process.

(13) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (10)～(12), its feature It is,

The apparent density of described Porous filler or the compound with oil absorption is 0.4g/cm³Above.

(14) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (10)～(13), its feature It is,

The content of described Porous filler in described (D) inorganic filling material or the compound with oil absorption is 0.1 volume %～the scope of 20 volume %.

(15) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (1)～(14), its feature It is,

And then as (D) inorganic filling material, containing choosing free Silicon stone, aluminium hydroxide, magnesium hydroxide, barium sulfate, carbonic acid At least one in the group that magnesium, brium carbonate are constituted.

(16) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (1)～(15), its feature It is,

Described (E) Chinese white is choosing free aluminium oxide, magnesium oxide, stibium oxide, titanium oxide, zirconium oxide, inorganic hollow grain At least one in the group that son is constituted.

(17) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (1)～(16), its feature It is,

The medium particle diameter of described (E) Chinese white is in the scope of 0.1～50 μm.

(18) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (1)～(17), its feature It is,

The use level described (D) inorganic filling material and described (E) Chinese white added up is relative to resin combination Total amount, in 10 volume %～the scope of 85 volume %.

(19) according to the luminous reflectance hot curing resin composition according to any one of above-mentioned (1)～(18), its feature It is,

Contain: (mixed in kneading to the various constituent of major general) temperature 20～100 DEG C, kneading time 10～30 minutes Under conditions of carry out mediating and the kneaded material that obtains.

(20) according to the luminous reflectance hot curing resin composition described in above-mentioned (19), it is characterised in that

Described kneaded material is after described kneading, obtains through ripening in 1～72 hour at 0～30 DEG C.

(21) manufacture method of a kind of luminous reflectance hot curing resin composition, it is characterised in that it is that manufacture is above-mentioned (1) method of the luminous reflectance hot curing resin composition～according to any one of (20), including:

Each composition of resin combination is at least mediated and forms the kneading process of kneaded material；

By described kneaded material at 0～30 DEG C through 1～72 hour the operation of ripening.

(22) according to the manufacture method of the luminous reflectance hot curing resin composition described in above-mentioned (21), its feature exists In,

Described kneading process is carried out under conditions of kneading temperature 20～100 DEG C and kneading time 10～30 minutes.

(23) a kind of optical semiconductor board for mounting electronic, it is characterised in that

It is to use the luminous reflectance hot curing resin composition according to any one of above-mentioned (1)～(20) to constitute 's.

(24) a kind of optical semiconductor board for mounting electronic, it is characterised in that it is to be formed with more than one to become light half Conductor element carries the optical semiconductor board for mounting electronic of the recess in region,

The inner circumferential side of the most described recess is by the luminous reflectance Thermocurable according to any one of above-mentioned (1)～(20) Resin combination is constituted.

(25) manufacture method of a kind of photosemiconductor board for mounting electronic, it is characterised in that

Described photosemiconductor board for mounting electronic is to be formed with more than one recess becoming optical semiconductor lift-launch region Optical semiconductor board for mounting electronic,

Utilize to recess described in major general and employ the luminous reflectance Thermocurable tree according to any one of claim 1～20 The transfer modling of oil/fat composition is formed.

(26) a kind of optical semiconductor device, wherein, at least possesses:

Optical semiconductor board for mounting electronic described in above-mentioned (24)；

The optical semiconductor carried in the recess bottom surface of described optical semiconductor board for mounting electronic；

By cover formed in described recess in the way of described optical semiconductor containing fluorophor transparent sealing resin layer.

Further, the application based on same Applicant in Japan's Patent 2006-309052 filed in 15 days November in 2006 Number, Japan's Patent 2007-098354 CLAIM OF PRIORITY filed in identical 4 days April in 2007, by referring to these explanations Book, group enters in the part of this specification.

Accompanying drawing explanation

Fig. 1 is the figure of an embodiment of the optical semiconductor board for mounting electronic representing the present invention, and (a) is axonometric chart, B () is side cut away view.

Fig. 2 is the skeleton diagram of the manufacture method of the optical semiconductor board for mounting electronic that the present invention is described, (a)～(c) is right Each operation in the case of should manufacturing substrate in utilizing transfer modling.

Fig. 3 is the figure of an embodiment of the optical semiconductor device representing the present invention, and (a) and (b) is to represent respective device The side cut away view of structure.

Fig. 4 is the figure schematically showing the flash mensuration mould used in embodiment, and (a) is side cut away view, (b) It it is top view.

The flash produced when Fig. 5 is the molding schematically showing and employing the flash mensuration mould shown in Fig. 4 Figure, (a) is side cut away view, and (b) is top view.

Detailed description of the invention

Hereinafter, embodiments of the present invention are described.The luminous reflectance hot curing resin composition of the present invention, its feature exists In, containing heat-curing resin composition and Chinese white, when molding under the condition of moulding being actually suitable for during molding, such as mould Mould temperature 100 DEG C～200 DEG C, below moulding pressure 20MPa and molding cycle under conditions of 60～120 seconds during transfer modling A length of below the 5mm of flash.It addition, the luminous reflectance that the wavelength after these heat cure is under 350nm～800nm be 80% with On.

The term " flash length during molding " used in this manual refers to: uses the flash shown in Fig. 4 to measure and uses Mould, when having carried out transfer modling, the die cavity from portion of mold center towards the upper die and lower die of mould mould assembling stitch gap, To the greatest length of the resin cured matter that radiation direction is overflowed.If such flash length is more than 5mm, then resin is dirty to light half Conductor element carries the peristome (recess) in region and highlights, and is likely to become fault when carrying optical semiconductor.Or, may Become the known methods such as utilization lead-in wire joint, electrical connection optical semiconductor and the fault of metal wiring.From semiconductor device For the viewpoint of workability during manufacture, flash length more preferably below the 3mm of the resin combination of the present invention, and then preferably Below 1mm.

The curable reflection resin combination of the present invention preferably considers to be applicable to the situation of transfer modling, it is possible in thermosetting Before change, at room temperature pressure moulding under (0～30 DEG C).More particularly, such as, under room temperature, 5～50MPa, about 1～5 second Under the conditions of can mold.For the viewpoint used with the purposes of optical semiconductor device, it is desirable to after heat cure, wavelength exists Luminous reflectance under 350nm～800mm preferably more than 80%, more preferably more than 90%.In the luminous reflectance situation less than 80% Under, the brightness of optical semiconductor device may be improved and can not play a role fully.

Hereinafter, the main composition composition of the luminous reflectance hot curing resin composition of the present invention is described.

In one embodiment of the present invention, (A) epoxy resin as heat-curing resin composition, is preferably comprised.(A) ring Epoxy resins without particular limitation of, as epoxy resin shaped material, it is possible to use commonly used resin.For example, it is possible to enumerate: will be with Phenol headed by phenol novolak type epoxy resin, o-cresol phenolic epoxy varnish and the novolaks tree of aldehydes The epoxidised resin of fat；Bisphenol-A, Bisphenol F, bisphenol S, alkyl replace the diglycidyl ether such as bis-phenol；Diamino-diphenyl first The glycidyl amine type epoxy resin that the reaction of the polyamine such as alkane, cyamelide and chloropropylene oxide obtains；Waited with peracetic acid Acid, the wire aliphatic epoxy resin that oxyalkylene key obtains；And cycloaliphatic epoxy resin etc..Be used alone these also can, or Share and two or more also may be used.The epoxy resin used is the most colourless or the most flaxen not relative to the resin of coloring.As that The epoxy resin of sample, for example, it is possible to enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, two Glycidyl isocyanuric acid ester, triglycidyl group isocyanuric acid ester.

In one embodiment of the present invention, as (A) epoxy resin, viscosity 100～150 DEG C at is preferably used is (G) oligomer of the scope of 100～2500mPa s.If the melt viscosity of the resin combination after Nie Heing is low, mobility is too high, Then may cause the air-hole blockage of molding die, residual air or volatile ingredient in mold cavity.The sky of residual in die cavity Gas or volatile ingredient become the reason that the shaping outward appearance such as space or weld mark is the most appropriate.It addition, the increase of adjoint molding number of times, The monomer component of solidfied material remained on surface is attached to molding die, pollutes mould.The knot of the attachment of monomer is piled up at mould Really, the imappropriate situation that the release property that the molded from mould occurs is deteriorated.In contrast, in the present invention, by making apparatus There is (G) oligomer of specific viscosity, by increasing capacitance it is possible to increase the melt viscosity of the resin combination after kneading, reduce mobility.It addition, By using such (G) oligomer, it is possible to reduce the residual monomer composition of the pollution cause becoming mould.Itself as a result, it is possible to Avoid the imappropriate situation occurred in the case of melt viscosity is low, it is possible to increase the transfer modling of resin combination, it is possible to Obtain the molded that outward appearance is superior.

(G) oligomer used in the present invention is by before the preparation of curable luminous reflectance resin combination, (A ') epoxy resin and (B ') firming agent and (C ') curing accelerator as required is at least coordinated to prepare.Above-mentioned (A ') Epoxy resin, above-mentioned (B ') firming agent, above-mentioned (C ') curing accelerator can use and (A) asphalt mixtures modified by epoxy resin formerly illustrated respectively The material that fat, aftermentioned peristome and (C) curing accelerator are identical.

More particularly, above-mentioned (G) oligomer such as can obtain through operation as described below, it may be assumed that will (A ') ring Epoxy resins and (B ') firming agent, relative to epoxy radicals 1 equivalent in this (A ') epoxy resin, allow to and this epoxy reaction Should coordinate with becoming below 0.3 equivalent by active group (anhydride group or hydroxyl) in (B ') firming agent, mediate to becoming argillaceous.Excellent Choosing arrange the argillaceous kneaded material that obtains then in the range of temperature 25～60 DEG C through the operation of ripening in 1～6 hour.Separately Outward, in the case of using (C ') curing accelerator, preferably with respect to (A ') epoxy resin and the summation 100 of (B ') firming agent Weight portion so that it is coordinate with becoming 0.005～0.05 weight portion.

(G) oligomer prepared as described above in order to reduce regulation molding time flash length, preferably 100～150 DEG C Under viscosity in the scope of 100～2500mPa s.Viscosity at more preferably 100 DEG C is in the scope of 100～2500mPa s.If (G) viscosity of oligomer is less than 100mPa s, then, when transfer modling, easily produce flash.On the other hand, if viscosity is more than 2500mPa s, then mobility when being in molding reduces, and mouldability becomes the tendency lacked.Further, make in this manual Term " viscosity " be the value that obtains of mensuration by employing ICI cone flap-type (U one Application プ レ mono-ト) viscometer.(G) Oligomer is become below 1mm by being crushed to its particle diameter, preserves, it is possible to suppress or stop in the environment of temperature less than 0 DEG C The only rising of viscosity.The breaking method use of oligomer utilizes the known any means such as the pulverizing of pottery mortar.

In one embodiment of the present invention, as heat-curing resin composition, contain containing while (A) epoxy resin (B) firming agent.(B) firming agent without particular limitation of, as long as the compound that can react with epoxy resin, but preferably its The firming agent of molecular weight 100～about 400.Additionally, it is preferred that it is colourless or the most flaxen not relative to the material of coloring.As tool The compound of body, can enumerate anhydride system firming agent, cyamelide derivant, phenol system firming agent etc..

As anhydride system firming agent, preferably there is the fusing point of more than 35 DEG C.As such anhydride, for example, it is possible to enumerate Anhydride phthalic acid, maleic anhydride, trihemellitic acid acid anhydride, PMA, hexahydro anhydride phthalic acid, tetrahydro anhydride phthalic acid, methyinorbornene Dicarboxylic anhydride, carbic anhydride, glutaric anhydride, dimethylated pentanedioic acid acid anhydride, diethyl glutarate acid anhydride, succinic anhydrides, methyl six Hydrogenation anhydride phthalic acid, methyltetrahydro anhydride phthalic acid etc..

As cyamelide derivant, can enumerate 1,3,5-tri-(1-carboxymethyl group) isocyanuric acid ester, 1,3,5- Three (2-carboxy ethyl) isocyanuric acid ester, 1,3,5-tri-(3-carboxypropyl) isocyanuric acid ester, 1, double (the 2-carboxyl second of 3- Base) isocyanuric acid ester etc..

As phenol system firming agent, can enumerate: by by phenol, cresol, resorcinol, catechol, bisphenol-A, bis-phenol Aphthols and formaldehyde, benzaldehyde, the water such as the phenol such as F, phenylphenol, amino-phenol and/or alpha-Naphthol, betanaphthol, dihydroxy naphthlene Yankee aldehyde etc. has the novolak phenolics that compound is condensed under acidic catalyst or cocondensation obtains of aldehyde radical；By Phenol and/or aphthols and dimethoxy xylol or the phenol aralkyl of double (methoxy) xenyl synthesis The aralkyl-type phenol resin such as resin, biphenyl type phenol aralkyl resin, naphthols aralkyl resin；Utilize phenol and/ Or the copolymerization of aphthols and bicyclopentadiene synthesize dicyclopentadiene-type phenol novolak type resin, dicyclopentadiene-type The dicyclopentadiene type phenol resins such as naphthol novolac varnish gum；Triphenyl methane type phenolic resin；Terpene modified phenolic resin； Xylol and/or meta-xylene phenol-formaldehyde resin modified；Melamine-modified phenolic resin；Cyclopentadiene phenol-formaldehyde resin modified；And altogether The phenolic resin etc. that poly-two of which is derived above.

In the firming agent formerly illustrated, choosing free anhydride phthalic acid, trihemellitic acid acid anhydride, hexahydro anhydride phthalic acid, tetrahydrochysene are preferably used Change anhydride phthalic acid, methylhexa-hydro anhydride phthalic acid, methyltetrahydro anhydride phthalic acid, glutaric anhydride, dimethylated pentanedioic acid acid anhydride, diethyl penta 2 The anhydride and 1 of the group that anhydride and cyclohexanetricarboxylic acid's acid anhydride are constituted, the trimerization such as 3,5-tri-(3-carboxypropyl) isocyanuric acid ester At least one party of Carbimide. derivant.These are possible not only to be used alone, it is also possible to share two or more.

In one embodiment of the present invention, as (B) firming agent, preferably at least use cyamelide derivant, more The anhydride combination of these and anhydride is especially had more than 35 DEG C fusing point is preferably used and uses.Cyamelide derivant Triazine skeleton, compared with common ring-type methylene skeleton, has the feature being difficult to be aoxidized by active oxygen.Therefore, by using Cyamelide derivant, gives previous feature to resin combination, it is possible to increase the resin combination after molding heat-resisting Property.In addition it is possible to utilize triazine skeleton and trifunctional's reactive group, improve the mechanical property of moulding bodies.And then, by inciting somebody to action Cyamelide derivant combines with anhydride, by increasing capacitance it is possible to increase the melt viscosity of resin combination, it is possible to when molding, suppression is from mould The flash length that tool is prominent.The match ratio of cyamelide derivant and anhydride can in the range of 1: 0～1: 10 suitably Adjust.For the viewpoint of the reduction of reflectance caused from the flavescence of cost cutting and suppression resin, preferably 1: 1～1: 3 join Composition and division in a proportion.

In another embodiment of the present invention, as (B) firming agent, preferably at least use cyclohexanetricarboxylic acid's acid anhydride.Logical Cross the use of cyclohexanetricarboxylic acid's acid anhydride, by increasing capacitance it is possible to increase the melt viscosity of resin combination, it is possible to shorten flash length during molding. It addition, can hardening time of shortening resin combination, it is thus possible to enough improve mould efficiency.As cyclohexanetricarboxylic acid The concrete example of acid anhydride, can enumerate the compound represented by following structural formula (I).

[changing 2]

With cyclohexanetricarboxylic acid's acid anhydride together, as (B) firming agent, other anhydride, the cyamelide formerly illustrated is share Derivant and phenol system firming agent etc. also may be used.As the firming agent share, mobility when molding and the coloring of molded For viewpoint, preferably anhydride phthalic acid, trihemellitic acid acid anhydride, hexahydro anhydride phthalic acid, tetrahydro anhydride phthalic acid, hydrogenated methyl base anhydride phthalic acid, first Base tetrahydro anhydride phthalic acid, glutaric anhydride, dimethylated pentanedioic acid acid anhydride, diethyl glutarate acid anhydride or 1,3,5-tri-(3-carboxypropyl) Isocyanuric acid ester.(B) as long as the containing ratio of cyclohexanetricarboxylic acid's acid anhydride in firming agent is capable of the purpose of the present invention, just Without particular limitation of, but preferably regulate in scope below 5 mass % and below 100 mass %.From cost and the balance of performance Viewpoint for, the scope more than above-mentioned containing ratio preferably 25 mass % and below 75 mass %.

(A) match ratio of epoxy resin and (B) firming agent is not in the case of (A) epoxy resin contains (G) oligomer, Preferably with respect to epoxy radicals 1 equivalent in (A) epoxy resin, it is possible to the active group in (B) firming agent of this epoxy reaction (anhydride group or hydroxyl) is the ratio of 0.5～1.5 equivalents.More preferably become the ratio of 0.7～1.2 equivalents.At above-mentioned active group In the case of 0.5 equivalent, the curing rate of composition epoxy resin is slack-off, and, the vitrification temperature of the solidfied material obtained Degree reduces, and sometimes can not get sufficient elastic modelling quantity.It addition, in the case of above-mentioned active group is more than 1.2 equivalents, sometimes solidify After intensity reduce.

On the other hand, as (A) epoxy resin, it is used alone (G) oligomer, or share (G) oligomer and (A) asphalt mixtures modified by epoxy resin In the case of fat, the match ratio of (A) epoxy resin (or (G) oligomer) and (B) firming agent is preferably with respect in (A) epoxy resin Epoxy radicals 1 equivalent, it is possible to the active group (anhydride group or hydroxyl) in (B) firming agent of this epoxy reaction become 0.5～ The ratio of 0.7 equivalent.More preferably become the ratio of 0.6～0.7 equivalent.In the case of above-mentioned activating agent is less than 0.5 equivalent, ring The curing rate of epoxy resin composition is slack-off, and, the vitrification point of the firming body obtained reduces, and sometimes can not get composition Elastic modelling quantity.It addition, in the case of above-mentioned active group is more than 0.7 equivalent, the intensity after solidification reduces sometimes.Further, (A) ring The equivalents that epoxy resins contains (B) firming agent in the case of (G) oligomer is (A ') epoxy by containing in (G) oligomer The total amount of the epoxy radicals contained respectively in resin and (A) epoxy resin is set to 1, in contrast, (B ') firming agent and (B) solidified Contain in agent above-mentioned can convert as equivalents with the summation of the active group of above-mentioned epoxy reaction.

In the luminous reflectance hot curing resin composition of the present invention, as required, as (C) curing accelerator, contain Suitable compound also may be used.It is, for example possible to use: 1,8-diaza-bicyclo-(5,4,0) endecatylene-7, triethylene diamine and Three-2, the tertiary amines such as 4,6-dimethylaminomethyl phenol；The imidazoles such as 2-ethyl-4 Methylimidazole. and 2-methylimidazole；Triphen Base phosphine, tetraphenyl tetraphenyl borate salts, four-normal-butyl-o, o-diethyl dithiophosphate, four-normal-butyl-tetrafluoro The phosphorus compounds such as borate, four-normal-butyl-tetraphenyl borate salts；Quaternary ammonium salt；Organic metal salt；And these derivant Deng.These be used alone also can, or share and also may be used.In these curing accelerators, tertiary amines, imidazoles, phosphatization are preferably used Compound.

The containing ratio of above-mentioned (C) curing accelerator relative to (A) epoxy resin, preferably 0.01～8.0 weight %, more preferably 0.1～3.0 weight %.If the containing ratio of curing accelerator is less than 0.01 weight %, the most sometimes can not get sufficiently solidifying promotion Effect.If it addition, containing ratio is more than 8.0 weight %, the most sometimes manifesting variable color at the moulding bodies obtained.

The luminous reflectance hot curing resin composition of the present invention, in order to regulate its mouldability, preferably comprises that (D) is inorganic to be filled out Fill material.(D) inorganic filler without particular limitation of, but it is, for example possible to use choosing free Silicon stone, aluminium hydroxide, magnesium hydroxide, sulfur At least one in the group that acid barium, magnesium carbonate, brium carbonate are constituted.Come from the viewpoint of heat conductivity, reflective character and mouldability Say, preferably at least contain Silicon stone.It addition, in order to improve flame retardancy, preferred compositions aluminium hydroxide and use.

In one embodiment of the present invention, as (D) inorganic filler, preferably comprise Porous filler or there is suction The compound of oiliness.As (D) inorganic filler, it is also possible to use Porous filler or choosing freely to have the silicon of oil absorption At least one in the group that stone, aluminium hydroxide, magnesium hydroxide, barium sulfate, magnesium carbonate, brium carbonate are constituted.Furthermore it is also possible to use There is porous structure, also there is the compound of oil absorption.As Porous filler or the shape of the compound with oil absorption Shape, without particular limitation of, it is, for example possible to use spherical shape, broken shape, discoid, bar-shaped, fibrous etc..Considering transfer modling Time mould in mobility in the case of, preferably spherical shape, broken shape, more preferably spherical shape.

It addition, the surface of above-mentioned Porous filler or the compound with oil absorption has been carried out physical property or chemical Hydrophilicity-imparting treatment or hydrophobization process also may be used.Preferred surface has been carried out hydrophobization process, more preferably makes oil absorption (according to JIS The ormal weight of K5101) become 50ml/100g and carry out chemical hydrophobization process with Shangdi.By using surface to be dredged The Porous filler of hydration process or have the compound of oil absorption, increases the bonding of (A) epoxy resin or (B) firming agent Property, its result, improves mobility during mechanical strength or the transfer modling of thermosetting compound.It addition, make oil absorption become by use The Porous filler that hydrophobization processes or the compound with oil absorption, energy has been carried out for more than 50ml/100g ground surface Enough cementabilities improved with (A) epoxy resin, further, it is possible to the effective time (pot of the resin combination after suppression kneading Life) reduce.It addition, when heat cure, additionally it is possible to suppression coloring.Fill out as the Porous implementing the process of such hydrophobization Fill agent, for example, it is possible to enumerate plug sieve river Bick (サ イ that Fuji Silesia (Fuji シ リ シ ア) KCC sells ロ ホ mono-PVC Star Network) 702.

It addition, above-mentioned Porous filler or have oil absorption compound apparent density without particular limitation of, but preferably 0.4g/cm³Above, according to claim preferably 0.4～2.0g/cm³.Further, apparent density refers to: consider Porous filler Or the density shared by the raw material of the compound with oil absorption and the density of the space shared by minute aperture (i.e. pore volume). In this apparent density less than 0.4g/cm³In the case of, the mechanical strength of filler particles is little, produces at agitating roller grinding machine etc. and cuts off During the melt kneading of power, particle may be caused to destroy.On the other hand, in apparent density more than 2.0g/cm³In the case of, at molding When the tablet of transfer modling, inclining of resin combination is easily adhered on the surface of the mould being in mortar mould and pestle mould composition To.

It addition, above-mentioned Porous filler or there is mean diameter preferably 0.1～100 μm of compound of oil absorption, examine Consider and the scope of more preferably 1～10 μm in the case of filler (the パ Star キ Application グ) efficiency of Chinese white.If mean diameter is more than 100 μm, or less than 0.1 μm, then, during melted when transfer modling, be in the tendency that the mobility of resin combination is deteriorated.

It addition, above-mentioned Porous filler or there is the specific surface area preferably 100～1000m of compound of oil absorption²/ g, More preferably 300～700m²/g.If specific surface area is less than 100m²/ g, then the oil absorption of the resin that filler causes diminishes, at tablet During molding, it is in pestle mould and easily adheres to the tendency of resin, if specific surface area is more than 1000m²/ g, then when being in transfer modling Melted time, be in resin combination mobility be deteriorated tendency.

It addition, above-mentioned Porous filler or have oil absorption compound content without particular limitation of, but the most relative It is 0.1 volume %～the scope of 20 volume % in (D) inorganic filler total amount.If the molding of resin combination when considering melted Property, the most more preferably 1 volume %～5 volume %.In the case of this content is less than 0.1 volume %, a part for resin combination It is liable to stick to the surface of the molding die of mortar mould and pestle mould, in the case of more than 20 volume %, melting when transfer modling When melting, it is in the tendency that the mobility of resin combination reduces.Such as, as above-mentioned Porous filler, use above-mentioned plug sieve In the case of river Bick 702, it contains the viewpoint of intensity of the mobility when resin combination melted or resin combination For, preferably 5 below volume %.

As (E) Chinese white used in the present invention, without particular limitation of, it is possible to use known Chinese white.Example As, it is possible to use aluminium oxide, magnesium oxide, stibium oxide, titanium oxide, zirconium oxide, inorganic hollow particle etc..Inorganic hollow particle is such as Water soda glass, aluminum silicate glass, sodium borosilicate glass, silicone rubber (シ ラ ス) etc. can be enumerated.From heat conductivity, luminous reflectance For the aspect of characteristic, preferably at least use aluminium oxide or magnesium oxide, or combine these and use.(E) particle diameter of Chinese white Preferred center particle diameter is in the scope of 0.1～50 μm.If this medium particle diameter is less than 0.1 μm, then it is in particle and easily condenses, dispersibility The tendency being deteriorated.On the other hand, if medium particle diameter is more than 50 μm, then the luminous reflectance that may not obtain solidfied material fully is special Property.(E) use level of Chinese white without particular limitation of, but be 10 volume %～85 bodies preferably with respect to resin combination total amount The scope of long-pending %.

The total use level of above-mentioned (D) inorganic filler and above-mentioned (E) Chinese white without particular limitation of, but the most relative It is 10 volume %～the scope of 85 volume % in resin combination total amount.If this total use level is less than 10 volume %, then may The reflective character of solidfied material can not be obtained fully.If it addition, amount to use level more than 85 volume %, then resin combination Mouldability is deteriorated, and is in the tendency of the making being difficult to photosemiconductor board for mounting electronic.

In the luminous reflectance hot curing resin composition of the present invention, (F) coupling agent can be added as required.(F) Coupling agent without particular limitation of, but it is, for example possible to use silane system coupling agent or titanate esters system coupling agent etc..As silane coupling Agent, it is, for example possible to use epoxy silane system, amino silicone methane series, cationic silane system, vinyl silanes system, silicon Acrylote methane series, Hydrosulphonyl silane system and these compound system etc..(F) kind of coupling agent or treatment conditions without particular limitation of, be suitable for resin combination The method directly added in thing or be pre-mixed inorganic filler or Chinese white and the method etc. added began to use from the past Method also may be used.(F) use level of coupling agent is below 5 weight % preferably with respect to resin combination.

It addition, in the luminous reflectance hot curing resin composition of the present invention, as the purpose of melt viscosity regulation, add Add (H) thickening agent also may be used.As (H) thickening agent, without particular limitation of, but it is, for example possible to use can be as by moral mountain (ト Network ヤ マ, strain) the nanometer Silicon stone that obtains of West Road, Lyons (the レ オ ロ シ mono-Le) CP-102 that sells.As the addition of (H) thickening agent, 0.15 below volume % of the cumulative volume of preferred resin compositions.If (H) addition of thickening agent is more than 0.15 volume %, then damage Hinder mobility during resin combination melted, and, after hardening, the sufficient strength of materials may be can not get.It addition, (H) Thickening agent preferred center particle diameter be the nanoparticulate fillers of 1nm～1000nm, more preferably medium particle diameter be 10nm's～1000nm Nanoparticulate fillers.The medium particle diameter filler less than 1nm is in particle and easily condenses, and the tendency that dispersibility reduces, from characteristic For the most preferred.In the case of using such (H) thickening agent, as a part for (D) inorganic filler, use nano-silicon Stone also may be used.On the other hand, if adding the filler more than 1000nm, then the tendency that flash length does not reduces it is in, for characteristic The most preferred.Further, in the resin combination of the present invention, in addition to (H) thickening agent, as required, add oxidation retarder, The various additives such as releasing agent, ion supplement.

The luminous reflectance hot curing resin composition of the present invention can be by the above-mentioned each composition of uniformly dispersing mixing Obtain, its preparation mechanism or condition etc. without particular limitation of.As usual way, can enumerate and utilize agitator etc., will regulation After the various compositions of use level fully and equably stir and mix, use agitating roller, extruder, kneader, roller and extruder Etc. mediating, and then by the kneaded material cooling obtained and the method pulverized.Further, about the form of kneading, limit the most especially Fixed, but preferred molten is mediated.The condition of melt kneading suitably can determine according to the kind of the composition used or use level, Without particular limitation of.For example, it is preferable to carried out melt kneading in the range of 15～100 DEG C through 5～40 minutes, more preferably 20～ Melt kneading was carried out through 10～30 minutes in the range of 100 DEG C.If temperature during melt kneading is less than 15 DEG C, then it is difficult to melt Mediate each composition, be in the tendency that dispersibility also reduces.On the other hand, in the case of the temperature higher than 100 DEG C, resin combination The macromolecule of thing quantifies progress, may cause resin composition.If it addition, the time of melt kneading is less than 5 minutes, then locating In can not effectively suppress the tendency of flash length, if being longer than 40 minutes, then the macromolecule of resin combination quantifies progress, may Resin combination is caused to solidify before molding.

The luminous reflectance hot curing resin composition of the present invention is preferably after coordinating, mediating above-mentioned each composition, for carrying The purpose of melt viscosity during high molding, carries out aging placement (ripening).More particularly, ripening is preferably at 0 DEG C～30 DEG C Implemented through 1～72 hour.Ripening more preferably at 15 DEG C～30 DEG C through 12～72 hours, and then preferably at 25 DEG C～30 Implemented through 24～72 hours at DEG C.In the case of being shorter than the ripening of time of 1 hour, it is in and can not effectively suppress excessive The tendency of material length, if carrying out being longer than the ripening of 2 hours, then when transfer modling, it may not be possible to guarantee sufficient mobility.Separately Outward, in the case of implementing ripening at a temperature of less than 0 DEG C, cause (C) curing accelerator torpescence, resin combination Three-dimensional cross-linked reaction is in progress deficiently, and viscosity time melted may not rise.It addition, implement at a temperature of higher than 30 DEG C In the case of ripening, resin combination absorbs moisture, and be in that the mechanical properties such as intensity or elastic modelling quantity of solidfied material is deteriorated inclines To.

The optical semiconductor board for mounting electronic of the present invention is characterised by, uses the luminous reflectance Thermocurable of the present invention Resin combination is constituted.Specifically, can enumerate have become optical semiconductor carry region more than one recessed Portion, the inner circumferential side of at least the above recess is the substrate being made up of the luminous reflectance hot curing resin composition of the present invention.Fig. 1 Representing an embodiment of the optical semiconductor board for mounting electronic of the present invention, (a) is axonometric chart, and (b) is side cut away view.As Shown in Fig. 1, the optical semiconductor board for mounting electronic 110 of the present invention is characterised by having: reflector 103, comprise Ni/Ag The Wiring pattern (lead frame) of plating 104 and metal wiring 105 is integrated, and is formed and becomes optical semiconductor lift-launch region The structure of recess 200, the inner circumferential side of at least the above recess 200 is by the luminous reflectance hot curing resin composition of the present invention Constitute.

The manufacture method of the optical semiconductor board for mounting electronic of the present invention without particular limitation of, but for example, it is possible to by pass Luminous reflectance hot curing resin composition or its tablet moulding bodies of the present invention is manufactured for passing molding.Fig. 2 is that this is described The skeleton diagram of the manufacture method of bright optical semiconductor board for mounting electronic, Fig. 2 (a)～(c) are corresponding to utilizing transfer modling Manufacture each operation in the case of substrate.More particularly, shown in optical semiconductor board for mounting electronic such as Fig. 2 (a), utilize punching The known method such as sanction or etching, is formed metal wiring 105 by metal forming, and secondly, the mould 301 in regulation shape configures metal Distribution 105 (Fig. 2 (b)), the luminous reflectance heat-curing resin injecting the present invention from the resin inlet 300 of mould 301 combines Thing (fused mass of tablet moulding bodies).Preferably through 60～120 under mold temperature 170～190 DEG C, moulding pressure 2～8MPa Second, after making the resin composition of injection, take apart a die 301, little through 1～3 at after mature temperature 120 DEG C～180 DEG C Time, carry out heat cure.Secondly, can be by the reflector being made up of the luminous reflectance hot curing resin composition solidified 103 assigned positions becoming the recess 200 that optical semiconductor carries region surrounded around are implemented Ni/Ag plating 104 and are manufactured (Fig. 2 (c)).

The optical semiconductor device of the optical semiconductor board for mounting electronic employing the present invention is characterised by least having Standby: the optical semiconductor board for mounting electronic of the present invention；It is equipped on the light of the recess bottom surface of optical semiconductor board for mounting electronic Semiconductor element；By cover be formed in recess in the way of optical semiconductor containing fluorophor transparent sealing resin layer.Fig. 3 A () and Fig. 3 (b) are the side cut away view of an embodiment of the optical semiconductor device representing the present invention respectively.More particularly, In the optical semiconductor device shown in Fig. 3, the present invention optical semiconductor board for mounting electronic 110 become photosemiconductor unit Optical semiconductor 100, this light are carried in the assigned position, bottom of the recess (with reference to the reference marks 200 of Fig. 2) that part carries region Semiconductor element 100 and metal wiring 105 utilize method known to bonding wire 102 or pad 107 etc., plate 104 via Ni/Ag Electrical connection, utilizes the transparent sealing resin 101 comprising known fluorophor 106, covers this optical semiconductor 100.

Embodiment

Hereinafter, by embodiment, the present invention is described in detail in detail, but the present invention is not limited to these.Further, following each embodiment and The details of the composition used in each comparative example is as described below.

* 1: triglycidyl group isocyanuric acid ester (epoxide equivalent 100, Nissan Chemical company system, trade name TEPIC-S)

* 2: hexahydro anhydride phthalic acid (with Guang Chun medicine company system)

* 3:1,3,5-tri-(3-carboxypropyl) isocyanuric acid ester (chemical conversion industrial group of four countries system, the acid of goods name C3CIC)

* 4: cyclohexanetricarboxylic acid's acid anhydride (Mitsubishi Gas Chemical company system, goods name H-TMAn)

* 5: tetrahydro anhydride phthalic acid (A Ludeli magnetic (ア Le De リ Star チ) company's system)

* 6: hydrogenated methyl anhydride phthalic acid (chemical conversion industrial group of Hitachi trade name HN5500)

* 7: four-normal-butyl-0,0-diethyl dithiophosphate (Japan Chemical Industry company system, trade name: Radix Et Rhizoma Rhei Section woods (ヒ シ U one リ Application) PX-4ET)

* 8: trimethoxy epoxy silane (Dong Lidakening (レ ダ ウ U one ニ Application グ) company's system, trade name SH6040)

* 9: fatty acid ester (Ke Laiente (Network ラ リ ア Application ト) company's system, trade name Hei Jisitewakesi (ヘ キ ス ト ワ ツクス)E)

* 10: fatty ether (Japan Pei Teluolaite (ocean ペ ト ロ ラ イ ト) company's system, trade name outstanding Buddhist nun lentor (ユ ニトツクス)420)

* 11: fused silica (Denki Kagaku Kogyo kabushiki's system, trade name FB-301)

* 12: fused silica (Denki Kagaku Kogyo kabushiki's system, trade name Fb-950)

* 13: fused silica (A Dema Otto Dix company system, trade name SO-25R)

* 14: Porous spheroidal silica (non-(the サ イ ロ ス Off イ of Silesia chemical company of Fuji system, goods name plug Ross ア) C-1504) mean diameter: 3 μm, apparent density: 0.58g/ml, specific surface area: 300m²/g)

* 15: Porous amorphous Silicon stone is (Silesia chemical company of Fuji system, goods name Sai Luo river Bick 702, flat All particle diameters: 4 μm, apparent density: 0.48g/ml, specific surface area: 300m²/g)

* 16: Porous amorphous Silicon stone is (Silesia chemical company of Fuji system, goods name Sai Li West Asia 430, average Particle diameter: 4 μm, apparent density: 0.48g/ml, specific surface area: 300m²/g)

* 17: hollow-particle (Sumitomo 3M company system, trade name S60-HS)

* 18: aluminium oxide (A Dema Otto Dix company system, trade name AO-802)

* 19: nanometer Silicon stone (De Shan company system, CP-102)

(embodiment A1～A16 and Comparative examples A 1～A7)

1. the preparation of luminous reflectance hot curing resin composition

According to following Table A 1 to the mixing ratio shown in Table A 3, coordinate each composition, utilize blender, after mediating fully, Utilize agitating roller, under prescribed conditions, melt kneading, obtain kneaded material.And then, by pulverizing kneaded material, prepare enforcement respectively Example A1～A16 and the luminous reflectance hot curing resin composition of Comparative examples A 1～A7.Further, Table A 1～each one-tenth shown in Table A 3 The unit of the use level divided is weight portion.Empty hurdle in table represents the cooperation not having corresponding composition.

2. the evaluation of luminous reflectance hot curing resin composition

About embodiment A1 formerly prepared～A16 and each resin combination of Comparative examples A 1～A7, according to following Step, measures luminous reflectance and flash length.It addition, inquire into the lead-in wire joint molding the substrate that each resin combination obtains Property, and be evaluated.These results are shown in following Table A 1～Table A 3.

(luminous reflectance)

Molding die temperature 180 DEG C, moulding pressure 6.9MPa, under conditions of 90 seconds hardening times, transfer modling is formerly After each luminous reflectance hot curing resin composition of preparation, through 2 hours at 150 DEG C, solidify after carrying out, thus distinguish The test piece of preparation thickness 1.0mm.Secondly, use integrating sphere spectrophotometer V-750 type (Japan Spectroscopy Corporation's system), survey The luminous reflectance of each test piece under the long 400nm of standing wave.

(flash length)

Use tank, make each luminous reflectance hot curing resin composition formerly prepared flow into flash (バ リ) and measure use Mould (with reference to Fig. 4), next solidifies, thus molded resin composition.Further, mold temperature during molding is 180 DEG C, mould Blow pressure is 6.9MPa, and the inlet time (passing time) of resin is 10 seconds, and solidification temperature is 180 DEG C, and hardening time is 90 seconds. After molding, unload the upper mold of flash mensuration mould, use slide calliper rule, measure when molding, at the upper die and lower die of mould The maximum of the length of the flash flow through in gap and produce.

The structure of the flash mensuration mould used when Fig. 4 is the mensuration schematically showing previous flash length, (a) For side cut away view, (b) is top view.As shown in Figure 4, flash mensuration mould includes a pair upper mold 400 and lower mold 401, on Mould 400 has resin inlet 402.It addition, lower mold 401 has: the die cavity 403 opposed with resin inlet 402；From die cavity 403 6 interspaces 404,405,406,407,408 and 409 extended towards mould peripheral part.The flash actually used measures to be used As shown in Figure 4, the profile of upper mold 400 and lower mold 401 is 140mm × 140mm to the size of mould, the upper footpath of resin inlet 402 For 7mm, lower footpath is 4mm, a diameter of 30mm of die cavity 403, and the degree of depth is 4mm.It addition, 6 interspaces 404 extended from die cavity 403 ～the width of 409 is respectively 5mm, the degree of depth is followed successively by 75,50,30,20,10 and 2 μm.Fig. 5 is to schematically show to employ Fig. 4 The figure of the flash produced during the molding of shown flash mensuration mould, (a) is side cut away view, and (b) is top view.Flash is such as Shown in Fig. 5, represent the part 410 that resin combination solidifies along the inflow of each gap from the extension of die cavity 403.In the present invention " the flash length " of regulation is to measure, with slide calliper rule, the value that the maximum of the flash represented by reference marks 410 obtains.

(evaluation of lead-in wire zygosity)

First, according to the manufacturing process shown in Fig. 2, each luminous reflectance heat-curing resin that transfer modling is formerly prepared Compositions, thus makes optical semiconductor board for mounting electronic.Further, condition of moulding is molding die temperature 180 DEG C, molding pressure Power 6.9MPa, hardening time 90 seconds, through 2 hours at 150 DEG C, solidify after enforcement.

Secondly, the optical semiconductor that becomes at the aforesaid substrate made carries the recess lift-launch optical semiconductor in region After, use wire bonder (HW22U-H, nine divisions of China in remote antiquity Matsushita Electric Ind. Co., Ltd. system, trade name) and the bonding wire of diameter 28 μm, Lead-in wire engages optical semiconductor and substrate, is thus electrically connected.The heating-up temperature of substrate when lead-in wire engages is 180 DEG C. Lead-in wire zygosity is to use Pood Su Te (プ Le テ ス タ mono-) PTR-01 (Co., Ltd.'s Leix card (レ ス カ) system, commodity Name), measure the tenacity of the lead-in wire of the lead-in wire joint of electrical connection optical semiconductor and substrate, about its value, according to following Metewand is evaluated.

The metewand of lead-in wire zygosity

◎: more than tenacity 10g

Zero: tenacity 4g is less than 10g

△: tenacity is less than 4g

×: can not engage

[table 1]

Table A 1

Table A 1 (Continued)

[table 2]

Table A 2

Table A 2 (Continued)

[table 3]

Table A 3

Table A 3 (Continued)

Resin combination according to Table A 1～Table A 3, embodiment A1～A16 shows superior reflective character, separately Outward, it is suppressed that flash length during transfer modling, superior lead-in wire zygosity is shown.Thus, use the luminous reflectance of the present invention to use Hot curing resin composition, in the case of manufacturing optical semiconductor board for mounting electronic or optical semiconductor device, it is not necessary to remove Go the operation that resin is dirty, therefore, highly beneficial in terms of the productivity ratio such as cost or manufacturing time.

(embodiment B1～B11 and comparative example B1～B8)

1. the preparation of luminous reflectance hot curing resin composition

According to the mixing ratio shown in following table B1 and table B2, coordinate each composition, utilize blender, after mediating fully, Utilize agitating roller, under prescribed conditions, carry out melt kneading, obtain kneaded material.And then, as required, to the kneaded material obtained After implementing ripening, cool down, pulverized, prepare embodiment B1～B11 and the luminous reflectance of comparative example B1～B8 the most respectively Use hot curing resin composition.

Further, the unit of the use level of each composition shown in table B1 and B2 is weight portion.It addition, the empty hurdle in table represents not There is the cooperation of corresponding composition, or do not implement corresponding operation.The details of each embodiment is as described below.

Embodiment B1 is directed to use with the method for specifically (G) oligomer.

Embodiment B2 relates to being set to 0.5 relative to the active group in the firming agent of epoxy radicals 1 equivalent in (A) epoxy resin ～0.7 method of scope of equivalent.

The method that embodiment B3 relates to adding Nano filling as (H) thickening agent.

Embodiment B4 relates to method by resin combination ripening under prescribed conditions.

Embodiment B5 relates to the method (kneading time extended to 30 minutes from 15 minutes) regulating melt kneading condition.

Embodiment B6～B11 relate to the situation share any two method in said method.

Further, (G) oligomer used in embodiment B1, B6, B7 and B9 is to prepare according to steps described below. It addition, for the viscosity of (G) oligomer, the ICI that use research equipment company limited (London) is made bores flap-type viscometer, at test portion Amount 0.155 ± 0.01g, the result measured at 100 DEG C are 1000mPa s.

(manufacture method of oligomer)

According to the matching requirements shown in table B1, coordinate each composition, utilize agitating roller, through 10 minutes at 25 DEG C, carry out Melt kneading.Further, the cooperation shown in table B1 becomes relative to epoxy radicals 1 equivalent, the ratio making anhydride group be 0.1 equivalent.Its Secondary, at 55 DEG C, through 4 hours, the argillaceous compositions (kneaded material) utilizing melt kneading to obtain is carried out ripening.Like that Ripening after, use bore 30mm ceramic mortar, kneaded material is crushed to particle diameter becomes below 1mm, is thus expected Oligomer.Preserve, in the environment of temperature less than 0 DEG C, the oligomer obtained.

2. the evaluation of luminous reflectance hot curing resin composition

Each luminous reflectance heat-curing resin group about embodiment B1 formerly prepared～B6 and comparative example B1～B8 Compound, identically with previous embodiment, measures luminous reflectance and flash length.It addition, identically with previous embodiment, visit Beg for the lead-in wire zygosity molding the substrate that each resin combination obtains, according to following benchmark, be evaluated.Those results are shown Go out in following table B1 and table B2.

(metewand of lead-in wire zygosity)

◎: more than tenacity 10g

Zero: tenacity 4g is less than 10g

△: tenacity is less than 4g

×: can not engage

[table 4]

Table B1

Table B1 (continuous 1)

Table B1 (continuous 2)

[table 5]

Table B2

Table B2 (Continued)

Resin combination according to table B1 and table B2, embodiment B1～A11 shows superior reflective character, separately Outward, it is suppressed that flash length during transfer modling, superior lead-in wire zygosity is shown.Therefore, the luminous reflectance using the present invention is used Hot curing resin composition, in the case of manufacturing optical semiconductor board for mounting electronic or optical semiconductor device, it is not necessary to remove Go the operation that resin is dirty, therefore, highly beneficial in terms of the productivity ratio such as cost or manufacturing time.It addition, it is oligomeric to employ (G) In the case of thing, it is possible to reduce the residual quantity of monomer component, therefore, in addition to can improving lead-in wire zygosity, additionally it is possible to keep away When exempting from so-called substrate molding mould is dirty and the not appropriate situation of the reduction of the release property of moulded work, obtain having superior The molding substrate of outward appearance.

(embodiment C1～C3 and comparative example C1, C2)

1. the preparation of luminous reflectance hot curing resin composition

According to the mixing ratio shown in following table C1, coordinating each composition, utilize blender, after mediating fully, utilization is stirred Mix roller, carry out melt kneading, thus obtain kneaded material.And then, the kneaded material obtained is cooled to room temperature, is pulverized, thus Preparation embodiment C1～C3, the luminous reflectance hot curing resin composition of comparative example C1 and C2 respectively.Further, shown in table C1 The unit of the use level of each composition is weight portion.It addition, the empty hurdle in table represents the cooperation not having corresponding composition.

2. the evaluation of luminous reflectance hot curing resin composition

About the luminous reflectance hot curing resin composition of embodiment C1 formerly prepared～C3 and comparative example C1, C2, Identically with previous embodiment, luminous reflectance and flash length are measured.It addition, identically with previous embodiment, mould is inquired into Mould the lead-in wire zygosity of the substrate that each resin combination obtains, according to following benchmark, be evaluated.Those results are shown in In following table C1.

(metewand of lead-in wire zygosity)

◎: more than tenacity 10g

Zero: tenacity 4g is less than 10g

△: tenacity is less than 4g

×: can not engage

[table 6]

Table C1

Table C (Continued)

Annotation: the poor flow quality of the resin in (*) mould, it is thus impossible to measure.

Luminous reflectance hot curing resin composition according to table C1, embodiment C1～C3 shows superior luminous reflectance Characteristic, it addition, flash length when inhibiting transfer modling, shows superior lead-in wire zygosity.C3CIC acid is due to its characteristic Chemical constitution, it is clear that the mechanical strength of moulding bodies can not only be improved, and, these suppress flash the most effectively.But It is, as firming agent, in the case of being used alone C3CIC acid, to be in the tendency that the mobility of compositions is deteriorated, thus, it can be known that Preferably it is applied in combination with other firming agent such as HHPA.Use the luminous reflectance hot curing resin composition of the present invention, manufacture light In the case of substrate for carrying semiconductor components or optical semiconductor device, it is not necessary to remove the operation that resin is dirty, therefore, becoming The productivity ratio aspects such as basis or manufacturing time are highly beneficial.

(embodiment D1～D5 and Comparative Example D 1～D3)

1. the preparation of luminous reflectance hot curing resin composition

According to the mixing ratio shown in following table D1, coordinating each composition, utilize blender, after mediating fully, utilization is stirred Mix roller, carry out melt kneading, thus obtain kneaded material.And then, the kneaded material obtained is cooled to room temperature, is pulverized, thus Preparation embodiment D1～D5, the luminous reflectance hot curing resin composition of Comparative Example D 1～D3 respectively.Further, shown in table D1 The unit of the use level of each composition is weight portion.It addition, the empty hurdle in table represents the cooperation not having corresponding composition.

2. the evaluation of luminous reflectance hot curing resin composition

About embodiment D1 formerly prepared～D5 and the luminous reflectance hot curing resin composition of Comparative Example D 1～D3, Identically with previous embodiment, luminous reflectance and flash length are measured.Further, in order to inquire into durability, the survey of luminous reflectance Surely it is that heating was implemented after 72 hours after the molding of test piece and at 150 DEG C.It addition, identically with previous embodiment, visit Beg for the lead-in wire zygosity molding the substrate that each resin combination obtains, according to following benchmark, be evaluated.Those results are shown Go out in following table D1.

(metewand of lead-in wire zygosity)

◎: more than tenacity 10g

Zero: tenacity 4g is less than 10g

△: tenacity is less than 4g

×: can not engage

[table 7]

Table D1

Table D1 (Continued)

Luminous reflectance hot curing resin composition according to table D1, embodiment D1～D5 shows superior luminous reflectance Characteristic, it addition, flash length when inhibiting transfer modling, shows superior lead-in wire zygosity.And then also know that, solidfied material The reflective character of (molding substrate) is difficult to aging.Therefore, the luminous reflectance hot curing resin composition of the present invention, system are used In the case of making optical semiconductor board for mounting electronic or optical semiconductor device, it is not necessary to the operation that removing resin is dirty, therefore, In terms of the productivity ratio such as cost or manufacturing time highly beneficial.Additionally also know that, the luminous reflectance thermosetting of the application of the invention The property changed resin combination, additionally it is possible to efficiency manufactures the reflectance that can keep high in visible ray to nearultraviolet rays region well Optical semiconductor board for mounting electronic.

(embodiment E1～E8)

According to the mixing ratio shown in table E1, coordinate each composition, utilize blender, after mediating fully, utilize agitating roller, Carry out melt kneading, thus obtain kneaded material.And then, the kneaded material obtained is cooled to room temperature, is pulverized, join the most respectively The luminous reflectance hot curing resin composition of embodiment E1 processed～E8.Further, the details of each composition shown in table E1 is such as Upper described, the unit of each use level is weight portion.

About the luminous reflectance hot curing resin composition of embodiment E1 formerly prepared～E8, with previous embodiment In the same manner, luminous reflectance and flash length are measured.It addition, identically with previous embodiment, inquire into and mold each resin combination The lead-in wire zygosity of the substrate that thing obtains, according to following benchmark, is evaluated.Those results are shown in following table E1.

(metewand of lead-in wire zygosity)

◎: more than tenacity 10g

Zero: tenacity 4g is less than 10g

△: tenacity is less than 4g

×: can not engage

[table 8]

Table E1

Table E1 (Continued)

Luminous reflectance hot curing resin composition according to table E1, embodiment E1～E8 shows superior luminous reflectance Characteristic, it addition, the inhibition of flash during transfer modling is high, shows more superior lead-in wire zygosity.So, by suitably Combination coordinates each constituent, additionally it is possible to bar lead-in wire zygosity further.Thus, use the luminous reflectance Thermocurable of the present invention Resin combination, in the case of manufacturing optical semiconductor board for mounting electronic or optical semiconductor device, it is not necessary to removes resin dirty Dirty operation, therefore, highly beneficial in terms of the productivity ratio such as cost or manufacturing time.

It is clear that from above explanation, without departing from the spirit and scope of this invention, may be constructed extensively The embodiment that ground is different, in addition to the scope of the request that is defined in of the present invention, is not restricted to its specific embodiment.

Claims (5)

1. a luminous reflectance hot curing resin composition, described compositions is used for optical semiconductor board for mounting electronic, its Described in substrate be formed more than one become optical semiconductor carry region recess optical semiconductor carry use Substrate, the inner circumferential side of the most described recess is to be made up of described luminous reflectance hot curing resin composition,

It is used along with described (A) epoxy resin that described luminous reflectance hot curing resin composition contains (A) epoxy resin (B) firming agent, (C) curing accelerator, (D) inorganic filling material, (E) Chinese white and (F) coupling agent,

Under conditions of molding temperature 100 DEG C～200 DEG C, below moulding pressure 20MPa and molding cycle 60～120 seconds, transmission A length of below the 5mm of flash produced during molding,

The luminous reflectance under wavelength 350nm～800nm after heat cure is more than 80%,

Described (B) firming agent contains more than cyclohexanetricarboxylic acid's acid anhydride 5 mass % on the basis of the entire amount of this firming agent,

Described cyclohexanetricarboxylic acid's acid anhydride is the compound represented by following structural formula (I),

(A) epoxy resin and the match ratio of (B) firming agent, relative to epoxy radicals 1 equivalent in (A) epoxy resin, it is possible to institute State the ratio that active group is 0.5～1.5 equivalents in (B) firming agent of epoxy reaction,

(D) the total use level of inorganic filling material and (E) Chinese white is relative to resin combination total amount, be 10 volume %～ The scope of 85 volume %.

2. an optical semiconductor board for mounting electronic, it is characterised in that

It is to use the luminous reflectance hot curing resin composition described in claim 1 to constitute.

3. an optical semiconductor board for mounting electronic, it is characterised in that it is to be formed with more than one to become photosemiconductor unit Part carries the optical semiconductor board for mounting electronic of the recess in region,

The inner circumferential side of the most described recess is to be made up of the luminous reflectance hot curing resin composition described in claim 1 's.

4. the manufacture method of a photosemiconductor board for mounting electronic, it is characterised in that

Described photosemiconductor board for mounting electronic is to be formed with more than one to become the light that optical semiconductor carries the recess in region Substrate for carrying semiconductor components,

The transmission mould employing the luminous reflectance hot curing resin composition described in claim 1 is utilized to recess described in major general Mould and formed.

5. an optical semiconductor device, wherein, at least possesses:

Optical semiconductor board for mounting electronic described in claim 3；

The optical semiconductor carried in the recess bottom surface of described optical semiconductor board for mounting electronic；

By cover formed in described recess in the way of described optical semiconductor containing fluorophor transparent sealing resin layer.