CN108603010A

CN108603010A - Light reflection hardening resin composition and its solidfied material and optical semiconductor device

Info

Publication number: CN108603010A
Application number: CN201780010306.7A
Authority: CN
Inventors: 铃木弘世; 海老浦康贵
Original assignee: Daicel Chemical Industries Ltd
Current assignee: Daicel Corp
Priority date: 2016-02-12
Filing date: 2017-02-06
Publication date: 2018-09-28
Also published as: JP2017141415A; KR20180107227A; TW201739817A; WO2017138491A1

Abstract

The present invention provide can be formed with high light reflectivity and heat resistance and excellent in light-resistance, be not susceptible to light reflective through when the solidfied material that reduces, especially in the light reflection hardening resin composition that can significantly play said effect when compression forming forms solidfied material.The light reflection hardening resin composition of the present invention contains the silicone derivative (I) of cycloaliphatic epoxy (A), rubber particles (B), white pigment (C), inorganic filler (D), intramolecular isocyanuric acid derivative (H) and intramolecular with 1 or more oxirane ring with 2 or more epoxy groups, and containing curing agent (E) and curing accelerator (F) or curing catalysts (G), the composition is liquid at 25 DEG C.

Description

Light reflection hardening resin composition and its solidfied material and optical semiconductor device

Technical field

The present invention relates to light reflection hardening resin composition and its solidfied material, with the reflection formed by the solidfied material The optical semiconductor device of body and optical semiconductor.The Japan spy that the application was filed an application based on 2 12nd, 2016 in Japan It is willing to No. 2016-025329 to claim priority, and its content is incorporated herein.

Background technology

In recent years, single in various indoor or outdoors display boards, image reading light source, traffic signals, giant display In member etc., it is developed with the use for the light-emitting device (optical semiconductor device) that optical semiconductor (LED element) is light source.Make For such optical semiconductor device, it is however generally that, photosemiconductor member is carried on substrate (optical semiconductor board for mounting electronic) Part and optical semiconductor device made of further sealing the optical semiconductor using transparent sealing material has been popularized. On substrate in such optical semiconductor device, formed to improve the export efficiency of the light sent out by optical semiconductor For making the component (reflector) that light reflects.

For above-mentioned reflector, it is desirable that have high light reflective.In the past, the constituent material as above-mentioned reflector, Knowing has for example：So that inorganic filler etc. is scattered in and (is gathered with the polyamide that terephthalic acid units are necessary structural unit Phenyl-diformyl polyimide resin) in made of resin combination etc. (referring to Patent Documents 1 to 3).

In addition, the constituent material as above-mentioned reflector, additionally it has been known that there is for example：Contained comprising epoxy with special ratios The light reflection of the thermosetting resin of resin and the inorganic oxide of refractive index 1.6~3.0 is with compositions of thermosetting resin (referring to special Sharp document 4).Furthermore it is known that having for example：Containing thermosetting resin component and more than one filler ingredient and by thermosetting property The refractive index of resin component entirety is calculated with the specific refractivity of each filler ingredient and by the volume ratio of each filler ingredient The state modulator gone out in particular range light reflection with compositions of thermosetting resin (referring to patent document 5).

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2000-204244 bulletins

Patent document 2：Japanese Unexamined Patent Publication 2004-75994 bulletins

Patent document 3：Japanese Unexamined Patent Publication 2006-257314 bulletins

Patent document 4：Japanese Unexamined Patent Publication 2010-235753 bulletins

Patent document 5：Japanese Unexamined Patent Publication 2010-235756 bulletins

Invention content

Problems to be solved by the invention

There are following problems for the reflector made using the material described in above patent document 1~5：With height output In blue photosemiconductor, the optical semiconductor device that white photosemiconductor is light source, can reason semiconductor element send out light, heat and Xanthochromia etc. timely occurs and deteriorates, cause light reflective through when reduce.Further, with the use of lead-free solder, there is system The heating temperature in reflow process (Reflow Soldering process) when making light-emitting device becomes higher tendency, and in such manufacture work The heat applied in sequence can also cause that above-mentioned reflector timely deteriorates, light reflective reduces this problem.

For this purpose, present situation requires to be not easy to that light reflective occurs relative to more height output, shorter wavelengths of light or high temperature Through when the material of heat resistance and excellent in light-resistance that reduces.

In addition, above-mentioned reflector is typically to undergo transmission by using in the material (resin combination) for forming the reflector Molding, compression forming and manufacture.However, the previous resin combination for being used to form reflector is suitable for transfer molding mostly, The heat resistance of reflector thus formed by the resin combination is excellent, but the reflector formed by compression forming Heat resistance is mostly more bad.

Therefore, the purpose of the present invention is to provide can be formed with high light reflectivity and heat resistance and excellent in light-resistance, no Easily occur light reflective through when the solidfied material that reduces, particularly can significantly play when compression forming forms solidfied material Go out the light reflection hardening resin composition of said effect.

In addition, the other of the present invention are designed to provide that productivity is excellent, has high light reflectivity and heat resistance and fast light Property is excellent, be not susceptible to light reflective through when the solidfied material that reduces.

Further, it is of the invention it is other be designed to provide the brightness for being not susceptible to light through when reduce, reliability it is high Optical semiconductor device.

Further, for above-mentioned reflector, it is desirable that be applied in based on machining, temperature change (for example, such as returning Heating, changes in temperature cycle as stream process under extreme high heat etc.) etc. stress in the case of be tough, be not likely to produce cracking (crackle) (such characteristic is also known as " resistance to cracking ") etc..This is because, when reflector cracks, light can be caused anti- Penetrating property reduces (i.e. the export efficiency of light reduces), it is difficult to ensure the reliability of light-emitting device.

Solution to the problem

The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that, including alicyclic epoxy Close object (A), rubber particles (B), white pigment (C), inorganic filler (D), curing agent (E), curing accelerator (F), intramolecular The siloxanes of isocyanuric acid derivative (H) and intramolecular with 2 or more epoxy groups with 1 or more oxirane ring spreads out Biological (I), and be liquid light reflection hardening resin composition at 25 DEG C, or include cycloaliphatic epoxy (A), rubber Particle (B), white pigment (C), inorganic filler (D), curing catalysts (G), intramolecular have 1 or more oxirane ring Isocyanuric acid derivative (H) and intramolecular have the silicone derivative (I) of 2 or more epoxy groups, and are liquid light at 25 DEG C Reflection hardening resin composition can be formed with high light reflectivity and heat resistance and excellent in light-resistance, to be not susceptible to light anti- Penetrating property through when the solidfied material that reduces, above-mentioned effect can be significantly especially being played when compression forming forms solidfied material Fruit.It is completed the present invention is based on these opinions.

That is, the present invention provides a kind of light reflection hardening resin composition, containing cycloaliphatic epoxy (A), There is the isocyanuric acid of 1 or more oxirane ring to spread out for rubber particles (B), white pigment (C), inorganic filler (D), intramolecular Biological (H) and intramolecular have the silicone derivative (I) of 2 or more epoxy groups, and promote containing curing agent (E) and solidification Agent (F) or curing catalysts (G), the light reflection hardening resin composition are liquid at 25 DEG C.

Further, it is necessary monomer component that the above-mentioned rubber particles (B) of present invention offer, which include with (methyl) acrylate, Polymer, surface have hydroxyl and/or carboxyl, and the average grain diameter of above-mentioned rubber particles (B) is 10~500nm, maximum particle diameter is The light reflection hardening resin composition of 50~1000nm.

Further, it includes following formula (I-1) compound represented that the present invention, which provides above-mentioned cycloaliphatic epoxy (A), Light reflection hardening resin composition.

[chemical formula 1]

Further, the present invention provides the light that above-mentioned isocyanuric acid derivative (H) is following formula (III-1) compound represented Reflection hardening resin composition.

[chemical formula 2]

[in formula (III-1), R⁷And R⁸It is identical or different, indicate hydrogen atom or the alkyl of carbon atom number 1~8.]

Further, it is in titanium oxide, zirconium oxide, zinc oxide and barium sulfate that the present invention, which provides above-mentioned white pigment (C), At least one, above-mentioned inorganic filler (D) be in silica, aluminium oxide, silicon nitride, aluminium nitride and boron nitride extremely A kind of few light reflection hardening resin composition.

Further, the present invention provides above-mentioned light reflection hardening resin composition, uses or is compressed into for transfer molding Type resin combination.

Further, the present invention provides above-mentioned light reflection hardening resin composition, is reflector formation resin group Close object.

In addition, the present invention provides the solidfied material of above-mentioned light reflection hardening resin composition.

In addition, present invention offer at least has optical semiconductor and the light of the reflector formed by above-mentioned solidfied material is partly led Body device.

That is, the present invention relates to following proposals.

[1] a kind of light reflection hardening resin composition contains cycloaliphatic epoxy (A), rubber particles (B), white pigment (C), inorganic filler (D), intramolecular have 1 or more oxirane ring isocyanuric acid derivative (H), And intramolecular has a silicone derivative (I) of 2 or more epoxy groups, and containing curing agent (E) and curing accelerator (F) or Curing catalysts (G), the light reflection hardening resin composition are liquid at 25 DEG C.

[2] the light reflection hardening resin composition described in above-mentioned [1], wherein above-mentioned rubber particles (B) are with more The rubber particles of layer structure, the multilayered structure include at least one layer of core part and cladding the core part with caoutchouc elasticity Shell.

[3] the light reflection hardening resin composition described in above-mentioned [1] or [2], wherein above-mentioned rubber particles (B) packet Include the polymer for necessary monomer component with (methyl) acrylate.

[4] the light reflection hardening resin composition described in any one of above-mentioned [2] or [3], wherein constitute above-mentioned rubber In the polymer of the core part with caoutchouc elasticity of micelle (B), as monomer component, including (methyl) acrylate Meanwhile also including in combination selected from one or more of aromatic ethenyl compound, nitrile and conjugated diene.

[5] the light reflection hardening resin composition described in any one of above-mentioned [2]~[4], wherein constitute above-mentioned rubber In the polymer of the shell of micelle (B), also wrapped in combination while comprising (methyl) acrylate as monomer component Containing selected from one or more of hydroxyl monomer and carboxyl group-containing monomer.

[6] the light reflection hardening resin composition described in any one of above-mentioned [1]~[5], wherein above-mentioned rubber granule The surface of sub (B) has hydroxyl and/or carboxyl.

[7] the light reflection hardening resin composition described in any one of above-mentioned [1]~[6], wherein above-mentioned rubber granule The average grain diameter of sub (B) is 10~500nm, maximum particle diameter is 50~1000nm.

[8] the light reflection hardening resin composition described in any one of above-mentioned [1]~[7], wherein above-mentioned ester ring type Epoxide (A) includes aftermentioned formula (I) compound represented.

[9] the light reflection hardening resin composition described in any one of above-mentioned [1]~[8], wherein above-mentioned ester ring type Epoxide (A) includes aftermentioned formula (I-1) compound represented.

[10] the light reflection hardening resin composition described in any one of above-mentioned [1]~[9], wherein above-mentioned isocyanide Urea acid derivative (H) is aftermentioned formula (III) compound represented.

[11] the light reflection hardening resin composition described in any one of above-mentioned [1]~[10], wherein above-mentioned isocyanide Urea acid derivative (H) is aftermentioned formula (III-1) compound represented.

[12] the light reflection hardening resin composition described in any one of above-mentioned [1]~[11], wherein above-mentioned silica Alkane derivatives (I) are annular siloxane and/or intramolecular of the intramolecular with 2 or more epoxy groups with 2 or more epoxy groups Straight-chain siloxanes.

[13] the light reflection hardening resin composition described in any one of above-mentioned [1]~[12], wherein above-mentioned white Pigment (C) is selected from least one of titanium oxide, zirconium oxide, zinc oxide and barium sulfate.

[14] the light reflection hardening resin composition described in any one of above-mentioned [1]~[13], wherein above-mentioned inorganic Filler (D) is selected from least one of silica, aluminium oxide, silicon nitride, aluminium nitride and boron nitride.

[15] the light reflection hardening resin composition described in any one of above-mentioned [1]~[14], wherein above-mentioned silica Alkane derivatives (I) are silicone compounds shown in aftermentioned formula (IV).

[16] the light reflection hardening resin composition described in any one of above-mentioned [1]~[15], wherein relative to solid The content (use level) of the property changed resin combination (100 weight %), above-mentioned cycloaliphatic epoxy (A) is 0.1~60 weight Measure %, 0.3~50 weight % or 0.5~40 weight %.

[17] the light reflection hardening resin composition described in any one of above-mentioned [1]~[16], wherein relative to solid The content (use level) of the property changed resin combination (100 weight %), above-mentioned rubber particles (B) is 0.01~20 weight %, 0.05 ~15 weight % or 0.1~10 weight %.

[18] the light reflection hardening resin composition described in any one of above-mentioned [1]~[17], wherein relative to solid The content (use level) of the property changed resin combination (100 weight %), above-mentioned white pigment (C) is 0.1~50 weight %, 1~40 Weight % or 5~35 weight %.

[19] the light reflection hardening resin composition described in any one of above-mentioned [1]~[18], wherein relative to solid The property changed resin combination (100 weight %), the content (use level) of above-mentioned inorganic filler (D) be 10~90 weight %, 13~ 75 weight %, 15~70 weight % or 20~70 weight %.

[20] the light reflection hardening resin composition described in any one of above-mentioned [1]~[19], wherein relative to solid The content (use level) of the property changed resin combination (100 weight %), above-mentioned curing agent (E) is 1~40 weight %, 3~35 weights Measure % or 5~30 weight %.

[21] the light reflection hardening resin composition described in any one of above-mentioned [1]~[20], wherein relative to solid The property changed resin combination (100 weight %), the content (use level) of above-mentioned curing accelerator (F) be 0.0001~5 weight % or 0.001~1 weight %.

[22] the light reflection hardening resin composition described in any one of above-mentioned [1]~[21], wherein relative to solid The property changed resin combination (100 weight %), the contents (use level) of above-mentioned curing catalysts (G) be 0.0001~5 weight % or 0.001~1 weight %.

[23] the light reflection hardening resin composition described in any one of above-mentioned [1]~[22], wherein relative to solid The content (use level) of the property changed resin combination (100 weight %), above-mentioned isocyanuric acid derivative (H) is 0.05~15 weight Measure %, 0.1~10 weight % or 0.3~5 weight %.

[24] the light reflection hardening resin composition described in any one of above-mentioned [1]~[23], wherein relative to solid The property changed resin combination (100 weight %), the content (use level) of above-mentioned silicone derivative (I) be 0.1~30 weight %, 0.5~20 weight % or 1.0~10 weight %.

[25] the light reflection hardening resin composition described in any one of above-mentioned [1]~[24], is transfer molding With or compression forming resin combination.

[26] the light reflection hardening resin composition described in any one of above-mentioned [1]~[25], for the reflection bodily form At with resin combination.

[27] solidfied material of the light reflection hardening resin composition described in any one of above-mentioned [1]~[26].

[28] a kind of optical semiconductor device at least has optical semiconductor and by the light reflection described in [27] with admittedly The reflector that the solidfied material of the property changed resin combination is formed.

The effect of invention

The hardening resin composition of the present invention due to above-mentioned composition, being formed with high light reflectivity and Heat resistance and excellent in light-resistance, be not susceptible to light reflective through when the solidfied material that reduces, especially by by compression forming Said effect can be significantly played when forming solidfied material.Thereby, it is possible to provide be not susceptible to light brightness through when reduce, can The optical semiconductor device high by property.

Description of the drawings

[Fig. 1] shows the schematic diagram of an example of the optical semiconductor board for mounting electronic of the present invention.The figure (a) in left side is vertical The figure (b) of body figure, right side is sectional view.

[Fig. 2] shows the schematic diagram (sectional view) of an example of the optical semiconductor device of the present invention.

[Fig. 3] shows another schematic diagram (sectional view of the optical semiconductor device of the present invention；Feelings with radiating piece Condition).

[Fig. 4] shows another schematic diagram (feelings with radiating piece (cooling fin) of the optical semiconductor device of the present invention Condition).The figure (a) in left side is vertical view, and the figure (b) on right side is the A-A ' sectional views in (a).

Specific implementation mode

The light reflection of the present invention (is also referred to as " hardening resin composition of the invention ") with hardening resin composition It is that there is 1 containing cycloaliphatic epoxy (A), rubber particles (B), white pigment (C), inorganic filler (D), intramolecular The isocyanuric acid derivative (H) and intramolecular of the above oxirane ring have the silicone derivative (I) of 2 or more epoxy groups, And containing curing agent (E) and curing accelerator (F) or curing catalysts (G), combined for the curable resin of liquid at 25 DEG C Object.It should be noted that there is the isocyanuric acid derivative (H) of 1 or more oxirane ring to be known as above-mentioned intramolecular sometimes " isocyanuric acid derivative (H) ".In addition, there is the silicone derivative (I) of 2 or more epoxy groups to be known as intramolecular sometimes " silicone derivative (I) ".

In other words, hardening resin composition of the invention be comprising cycloaliphatic epoxy (A), rubber particles (B), White pigment (C), inorganic filler (D), curing agent (E), curing accelerator (F), isocyanuric acid derivative (H) and siloxanes spread out Biological (I) is the light reflection hardening resin composition of liquid as neccessary composition and at 25 DEG C, or includes ester ring type epoxy Compound (A), rubber particles (B), white pigment (C), inorganic filler (D), curing catalysts (G), isocyanuric acid derivative (H) and silicone derivative (I) as neccessary composition and at 25 DEG C be liquid hardening resin composition.It needs to illustrate Be, in hardening resin composition of the invention other than above-mentioned neccessary composition, can also as needed and include it is other at Point.It should be noted that the hardening resin composition of the present invention can be as can form cured thermosetting by heating Property composition (thermosetting epoxy resin composition) use.

It should be noted that in this specification, " light reflection hardening resin composition " refers to：It can be formed with light The hardening resin composition of reflexive solidfied material.Specifically refer to for example be formed the reflectivity of the light to wavelength 450nm For the hardening resin composition of the solidfied material of 50% or more (preferably 80% or more, more preferably 90% or more).

By make the present invention hardening resin composition at 25 DEG C be liquid, have suitable for compression forming tendency, Solidfied material (reflector) has light reflective excellent and the tendency of heat resistance and excellent in light-resistance.It should be noted that this theory In bright book, " being liquid at 25 DEG C " refers to, is under normal pressure that 1000000mPas or less (is preferably in the viscosity of 25 DEG C of measurement 800000mPas or less).It should be noted that Digital Viscometer (model " DVU-EII can be used for example in above-mentioned viscosity Type ", (strain) Tokimec systems), in rotor:Standard 1 ° of 34 ' × R24, temperature:25 DEG C, rotating speed:Under conditions of 0.5~10rpm into Row measures.

The hardening resin composition of the present invention at 25 DEG C for liquid for example can be by being used as ingredient (for example, alicyclic ring Formula epoxide (A), curing agent (E), curing accelerator (F), curing catalysts (G) etc.) using at 25 DEG C for liquid at Divide and is readily available.It should be noted that as mentioned component, the ingredient at 25 DEG C for solid can also be used, but it contains It is liquid that the hardening resin composition that should be adjusted so that the present invention, which is measured, at 25 DEG C.Furthermore it is also possible to by rubber particles (B), white pigment (C), inorganic filler (D) etc. are not destroying the effect of the present invention at 25 DEG C for the content of the ingredient of solid It is adjusted and is readily available in range.

[cycloaliphatic epoxy (A)]

Cycloaliphatic epoxy (the ester ring type asphalt mixtures modified by epoxy resin of the neccessary composition of hardening resin composition as the present invention Fat) (A), it is intramolecular (in a molecule) at least change with alicyclic ring (aliphatic hydrocarbon ring) structure and epoxy group (Oxyranyle) Object is closed, known or usual cycloaliphatic epoxy can be used.But it should be recognized that belonging to isocyanuric acid derivative (H) And those of silicone derivative (I) is not included in cycloaliphatic epoxy (A).As cycloaliphatic epoxy (A), More specifically, it can be mentioned, for example：(i) there is the epoxy group (alicyclic ring being made of adjacent 2 carbon atoms and oxygen atom for constituting alicyclic ring Formula epoxy group) compound, (ii) have directly with singly bound in the compound of the epoxy group of alicyclic ring.

There is the compound of ester ring oxygroup as above-mentioned (i), intramolecular can be used that there is 1 or more ester ring The known or usual compound of oxygroup, is not particularly limited.As above-mentioned ester ring oxygroup, from hardening resin composition Curability and solidfied material (reflector) heat resistance and light resistance from the viewpoint of, preferred epoxycyclohexyl.In particular, from solid From the viewpoint of the heat resistance and light resistance of compound (reflector), preferably intramolecular has the change of 2 or more epoxycyclohexyls Close object, more preferably following formula (I) compounds represented.

[chemical formula 3]

In formula (I), X indicates singly-bound or linking group (bivalent group with 1 or more atom).As above-mentioned linker Group, it can be mentioned, for example：Some or all of bivalent hydrocarbon radical, carbon-to-carbon double bond are through (" the epoxidation Asia alkene of alkenylene made of epoxidation Base " is also referred to as), carbonyl, ehter bond, ester bond, carbonate group, amide groups and by multiple bases to link in these groups Group etc..It should be noted that 1 or more that constitutes the carbon atom of the cyclohexane ring (epoxycyclohexyl) in formula (I) can also key Conjunction has the substituent groups such as alkyl.

As the compound that the X in formula (I) is singly-bound, 3,4,3', 4'- bicyclic oxygens connection hexamethylene etc. can be enumerated.

As above-mentioned bivalent hydrocarbon radical, can enumerate：The alkylidene of straight or branched that carbon atom number is 1~18, divalent Alicyclic type hydrocarbon etc..As carbon atom number be 1~18 straight or branched alkylidene, it can be mentioned, for example：Methylene, methyl Methylene, dimethylated methylene base, ethylidene, propylidene, trimethylene etc..As the alicyclic type hydrocarbon of above-mentioned divalent, can enumerate Such as：1,2- cyclopentylenes, 1,3- cyclopentylenes, cyclopentylidene, 1,2- cyclohexylidenes, 1,3- cyclohexylidenes, 1,4- cyclohexylidenes, Cycloalkylidenes such as cyclohexylidene (including cycloalkanes fork) etc..

As some or all of above-mentioned carbon-to-carbon double bond through the Asia in alkenylene made of epoxidation (epoxidation alkenylene) Alkenyl, it can be mentioned, for example：Ethenylidene, the third alkenylene, 1- butenylidenes, 2- butenylidenes, Aden's dialkylene, inferior pentenyl, The alkenylene etc. of the straight or brancheds of carbon atom numbers 2~8 such as sub- hexenyl, heptene base, sub- octenyl.In particular, conduct Above-mentioned epoxidation alkenylene, preferably carbon-to-carbon double bond all through alkenylene made of epoxidation, more preferably carbon-to-carbon double bond The alkenylene all through carbon atom number made of epoxidation 2~4.

As the linking group in above-mentioned X, the particularly preferably linking group containing oxygen atom is specific enumerable：- CO- ,-O-CO-O- ,-COO- ,-O- ,-CONH-, epoxidation alkenylene；By multiple groups to link in these groups； 1 or 2 or more in these groups with 1 or 2 or more the group etc. to link in bivalent hydrocarbon radical.As divalent hydrocarbon Base can enumerate example among the above and those of go out.

As the typical example of above-mentioned formula (I) compound represented, can enumerate：Change shown in following formula (I-1)~(I-10) Close object, bis- (3,4- 7-oxa-bicyclo[4.1.0-1- bases) propane of 2,2-, bis- (3,4- 7-oxa-bicyclo[4.1.0-1- bases) ethane of 1,2-, 1,2- rings Bis- (3,4- 7-oxa-bicyclo[4.1.0-1- bases) ethane of oxygen-1,2-, bis- (3,4- epoxycyclohexyl-methyls) ethers etc..Under it should be noted that State the integer that l, m in formula (I-5), (I-7) indicate 1~30 respectively.R in following formula (I-5) is the Asia of carbon atom number 1~8 Alkyl can be enumerated：Methylene, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene, sub- sec-butyl, pentylidene, Asia The alkylidene of the straight or brancheds such as hexyl, heptamethylene, octamethylene.In these, preferably methylene, ethylidene, propylidene, Asia are different The alkylidene of the straight or branched of the carbon atom numbers such as propyl 1~3.N1~n6 in following formula (I-9), (I-10) is indicated respectively 1~30 integer.

[chemical formula 4]

[chemical formula 5]

There is the compound of the epoxy group directly with singly bound in alicyclic ring as above-mentioned (ii), it can be mentioned, for example following Formula (II) compound represented (epoxy resin).

[chemical formula 6]

In above-mentioned formula (II), R¹Indicate p valence organic groups.P indicates 1~20 integer.As p valence organic groups, can arrange Citing is such as：The structure formed with the p hydroxyl of removal from the structural formula of the aftermentioned organic compound with p hydroxyl P valence organic groups etc..

In formula (II), q indicates 1~50 integer.It should be noted that in the case where p is 2 or more integer, multiple q It can be the same or different.The integer for being 3~100 with (summation) of q in formula (II).

In formula (II), R²For the substituent group on cyclohexane ring shown in formula, indicate shown in following formula (IIa)~(IIc) Arbitrary group in group.R on above-mentioned cyclohexane ring²Bonding position be not particularly limited, but in general, will be with oxygen atom It is 4 or 5 carbon atoms in the case that the position of 2 carbon atoms of the cyclohexane ring of bonding is set as 1,2.In addition, In the case that formula (II) compound represented has multiple cyclohexane rings, the R in each cyclohexane ring²Bonding position can phase It is same to can also be different.R in formula (II)²It is at least one for group (epoxy group) shown in formula (IIa).It should be noted that There are 2 or more R in formula (II) compound represented²In the case of, multiple R²It can be the same or different.

[chemical formula 7]

[chemical formula 8]

- CH=CH₂ (IIb)

[chemical formula 9]

In formula (IIc), R³It indicates hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted alkyl-carbonyl or takes Generation or unsubstituted aryl carbonyl.As abovementioned alkyl, it can be mentioned, for example：It is methyl, ethyl, n-propyl, isopropyl, butyl, different The alkane of the straight or brancheds of carbon atom numbers 1~20 such as butyl, sec-butyl, tertiary butyl, amyl, hexyl, octyl, 2- ethylhexyls Base etc..As abovementioned alkyl carbonyl, it can be mentioned, for example：Methyl carbonyl (acetyl group), ethylcarbonyl group, n-propyl carbonyl, isopropyl The straight or branched of the carbon atom numbers such as carbonyl, n-butylcarbonyl, butylcarbonyl, sec-butylcarbonyl group, tert-butyl carbonyl 1~20 Alkyl-carbonyl etc..As above-mentioned aryl carbonyl, it can be mentioned, for example：Phenylcarbonyl group (benzoyl), 1- naphthyl carbonyls, 2- naphthalenes Aryl-carbonyl of the carbon atom numbers such as base carbonyl 6~20 etc..

As the substituent group that above-mentioned alkyl, alkyl-carbonyl, aryl carbonyl optionally have, it can be mentioned, for example：Carbon atom The substituent group etc. of number 0~20 (more preferably carbon atom number 0~10).As above-mentioned substituent group, it can be mentioned, for example：Fluorine atom, chlorine The halogen atoms such as atom, bromine atom, iodine atom；Hydroxyl；Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy Equal alkoxies (preferably C_1-6Alkoxy, more preferably C_1-4Alkoxy)；The alkenyloxy groups such as allyloxy (preferably C_2-6Alkenyloxy group, More preferably C_2-4Alkenyloxy group)；The acyloxy such as acetoxyl group, propionyloxy, (methyl) acryloxy (preferably C_1-12Acyl-oxygen Base)；Sulfydryl；The alkylthio groups such as methyl mercapto, ethylmercapto group (preferably C_1-6Alkylthio group, more preferably C_1-4Alkylthio group)；Allyl sulfenyl etc. Alkenylthio group (preferably C_2-6Alkenylthio group, more preferably C_2-4Alkenylthio group)；Carboxyl；Methoxycarbonyl, ethoxy carbonyl, propoxyl group carbonyl The alkoxy carbonyls such as base, butoxy carbonyl (preferably C_1-6Alkoxy-carbonyl)；Amino；Methylamino, ethylamino, dimethyl The lists such as amino, diethylamino or dialkyl amido (preferably single or two-C_1-6Alkyl amino)；Acetyl-amino, propiono ammonia The acyl aminos such as base (preferably C_1-11Acyl amino)；The group of the oxygen heterocycle butyl such as ethyl oxa- cyclobutoxy group；Acetyl group, The acyl groups such as propiono；Oxo base；2 in these above according to needing via C_1-6Group made of alkylene etc..Separately Outside, the substituent group optionally having as above-mentioned aryl carbonyl, can also further enumerate above-mentioned substituted or unsubstituted alkyl, Above-mentioned substituted or unsubstituted alkyl-carbonyl.

Relative to the R in formula (II) compound represented²Total amount (100 moles of %), group (ring shown in formula (IIa) Oxygroup) ratio be not particularly limited, but preferably 40 moles of % or more (for example, 40~100 moles of %), more preferably 60 rub You are % or more, further preferably 80 moles of % or more.When aforementioned proportion is 40 moles of % or more, there are the heat-resisting of solidfied material The tendency that property, light resistance, mechanical property etc. further increase.It should be noted that aforementioned proportion can be for example, by¹H-NMR is composed The calculatings such as measurement, ethylene oxide oxygen concentration determination.

For formula (II) compound represented, though being not particularly limited, for example, it can manufacture as follows：With intramolecular Organic compound [R with p hydroxyl¹(OH)_p] it is initiator (that is, with hydroxyl (activation hydrogen) of the compound for starting point) 1,2- epoxy -4- vinyl cyclohexanes (3- vinyl -7- oxabicyclos [4.1.0] heptane) are made to carry out ring-opening polymerisation (cation Polymerization), then epoxidation is carried out using oxidant.

There is the organic compound [R of p hydroxyl as above-mentioned intramolecular¹(OH)_p], it can be mentioned, for example：Methanol, ethyl alcohol, third The aliphatic alcohols such as alcohol, butanol, amylalcohol, hexanol, octanol；Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, two Propylene glycol, 1,3 butylene glycol, 1,4- butanediols, pentanediol, 1,6-HD, neopentyl glycol, neopentyl glycol ester, hexamethylene diformazan Alcohol, glycerine, diglycerol, polyglycereol, trimethylolpropane, pentaerythrite, dipentaerythritol, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F, the polyalcohols such as A Hydrogenated Bisphenol A S；Polyvinyl alcohol, polyvinyl acetate partial hydrolystate, starch, acrylic polyol resin, benzene Ethylene-allyl alcohol copolymer resins, polyester polyol, polycaprolactone polyol, polytrimethylene polyalcohol, polytetramethylene glycol, Polycarbonate polyol class, the polybutadiene with hydroxyl, cellulose, cellulose acetate, cellulose acetate-butyrate, ethoxy are fine Tie up the oligomer or polymer etc. with hydroxyl such as cellulosic polymers such as element.

Above-mentioned 1,2- epoxies -4- vinyl cyclohexanes can utilize known or customary way to manufacture, and be not particularly limited, example Such as, 4 vinyl cyclohexene obtained from the dimerization through butadiene can be made to carry out by using oxidants such as Peracetic acid PART EPOXY and obtain.In addition, as 1,2- epoxy -4- vinyl cyclohexanes can also use commercially available product.

It in addition, as above-mentioned oxidant, can be used known in hydrogen peroxide, organic peroxide acid etc. or usual oxidant, do not have There is particular determination, and for example as organic peroxide acid, peroxyformic acid, Peracetic acid, benzoyl hydroperoxide, trifluoro peroxide second can be enumerated Acid etc..Wherein, Peracetic acid is due to industrially can inexpensively obtain and stability is also high, preferably.

It should be noted that above-mentioned ring-opening polymerisation and epoxidation are more specifically, can be according to such as Japanese Unexamined Patent Application 60- Known customary way described in No. 161973 bulletins etc. is implemented.

The weight average molecular weight of the standard polystyren conversion of formula (II) compound represented is not particularly limited, preferably 300~100000,1000~10000 are more preferably.When weight average molecular weight is 300 or more, there are the mechanical strengths of solidfied material, resistance to The tendency that hot, light resistance improves.On the other hand, weight average molecular weight be 100000 or less when, there are viscosity will not become it is excessively high, It is easy mobility when being molded being held in low-level tendency.It should be noted that weight average molecular weight can utilize gel infiltration Chromatography (GPC) method measures.

The equivalent (epoxide equivalent) of the epoxy group of formula (II) compound represented is not particularly limited, preferably 50~ 1000,100~500 are more preferably.When epoxide equivalent is 50 or more, there are the tendencies that solidfied material is not easy to become fragile.On the other hand, ring When oxygen equivalent is 1000 or less, there are the tendencies that the mechanical strength of solidfied material improves.It should be noted that epoxide equivalent can be based on JIS K7236:2001 are measured.

In the hardening resin composition of the present invention, cycloaliphatic epoxy (A) can be used alone, can also It is used in combination of two or more.In addition, cycloaliphatic epoxy (A) can both be manufactured by known or customary way, It can also use such as trade name " CELLOXIDE 2021P ", " CELLOXIDE 2081 " (above by (strain) Daicel systems) Commercially available product.

From the viewpoint of operability when preparing and when casting etc., cycloaliphatic epoxy (A) is preferably in room temperature (25 DEG C) under be in a liquid state.Even in addition, being the cycloaliphatic epoxy (A) of solid under room temperature (25 DEG C), as long as being in after engagement Liquid can also then contain.

Wherein, from the viewpoint of further increasing the light reflective of solidfied material (reflector), heat resistance and light resistance, this The hardening resin composition of invention preferably at least includes the compound that (i) has ester ring oxygroup, is more preferably further wrapped Have directly with singly bound in the compound of the epoxy group of alicyclic ring containing (ii).

The content (use level) of cycloaliphatic epoxy (A) in the hardening resin composition of the present invention is not special It limits, but relative to hardening resin composition (100 weight %), preferably 0.1~60 weight %, more preferably 0.3~50 Weight %, further preferably 0.5~40 weight %.By make cycloaliphatic epoxy (A) content be 0.1 weight % with On, there are the heat resistances of solidfied material (reflector) and light resistance there is the tendency further increased.On the other hand, by making alicyclic ring The content of formula epoxide (A) is 60 weight % hereinafter, there are the heat resistance of solidfied material (reflector) and light resistance are further It improves, the generation for a problem that linear expansion coefficient reduces, the warpage of lead frame on optical semiconductor board for mounting electronic The tendency being inhibited.

In the case of containing the epoxide other than cycloaliphatic epoxy (A), the curability relative to the present invention The cycloaliphatic epoxy (A) of the total amount (100 weight %) for the compound with epoxy group for including in resin combination Ratio is not particularly limited, such as preferably 1~90 weight %, more preferably 5~80 weight %, further preferably 10~70 Weight %.By the way that within the above range, there are the tendencies that the heat resistance of solidfied material (reflector) and light resistance further increase.It needs It is noted that as the compound with epoxy group for including in curable epoxy resin composition of the invention, can enumerate Such as：Cycloaliphatic epoxy (A), isocyanuric acid derivative (H) and silicone derivative (I) etc..

It should be noted that in the present specification, each ingredient (example for including in hardening resin composition of the invention Such as, cycloaliphatic epoxy (A), rubber particles (B), white pigment (C), inorganic filler (D), curing agent (E), solidification promote Into agent (F), curing catalysts (G), isocyanuric acid derivative (H), silicone derivative (I) etc.) content respectively can with protect Card total amount suitably selects in the range of 100 weight % modes below are from record.

[rubber particles (B)]

The rubber particles (B) of the neccessary composition of hardening resin composition as the present invention are the grains for having caoutchouc elasticity Son.The hardening resin composition of the present invention is by by rubber particles (B) and cycloaliphatic epoxy (A), white pigment (C), inorganic filler (D), isocyanuric acid derivative (H) and silicone derivative (I) are applied in combination, and exist and are formed by admittedly The light reflective of compound, heat resistance, light resistance and resistance to cracking are excellent, are especially forming solidfied material by compression forming When can significantly play the tendency of said effect.

As rubber particles (B), from favorable dispersibility and it is easy to get the effect that toughness improves (resistance to cracking raising) Viewpoint is set out, it is however preferred to have is formed by least one layer of shell of core part and cladding the core part with caoutchouc elasticity more The rubber particles (hereinafter also referred to " nucleocapsid type rubber particle ") of layer structure (nucleocapsid).From further increasing the resistance to of solidfied material From the perspective of hot and light resistance, rubber particles (B) include particularly preferably with (methyl) acrylate for necessary monomer The polymer (condensate) of ingredient, surface have hydroxyl and/or carboxyl (in hydroxyl and carboxyl any one or both) conduct The rubber particles for the functional group that can be reacted with compounds with epoxy group such as cycloaliphatic epoxies (A).That is, rubber granule Sub (B) particularly preferably includes the polymer (acrylic polymer) for necessary monomer component with (methyl) acrylate Nucleocapsid type rubber particle.It should be noted that in the hardening resin composition of the present invention, rubber particles (B) can be independent Using one kind, can also be used in combination of two or more.

In the case that rubber particles (B) are nucleocapsid type rubber particle, the poly- of the above-mentioned core part with caoutchouc elasticity is constituted It closes object to be not particularly limited, preferably includes (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate Polymer Deng (methyl) acrylate as necessary monomer component.In addition, constituting the above-mentioned core part with caoutchouc elasticity Polymer can also include the aromatic ethenyl such as styrene, α-methylstyrene；Acrylonitrile, methacrylonitrile etc. Nitrile；Butadiene, isoprene equiconjugate diene；Alpha-olefins such as ethylene, propylene, isobutene etc. are used as monomer component.

Wherein, in the polymer for constituting the above-mentioned core part with caoutchouc elasticity, as monomer component, preferably comprising Combination is comprising selected from one or both of aromatic ethenyl compound, nitrile and conjugated diene while (methyl) acrylate More than.That is, as the polymer for constituting above-mentioned core part, it can be mentioned, for example：(methyl) acrylate/aromatic vinyl closes The bipolymers such as object, (methyl) acrylate/conjugated diene；(methyl) acrylate/aromatic ethenyl compound/conjugation Terpolymers such as diene etc..It should be noted that the polymer for constituting above-mentioned core part can also include polydimethylsiloxanes The polysiloxanes such as alkane, polyphenyl methyl siloxane, polyurethane etc..

In the polymer for constituting above-mentioned core part, as other monomer components, divinylbenzene, (methyl) can also be contained Allyl acrylate, ethylene glycol two (methyl) acrylate, diallyl maleate, triallyl cyanurate, phthalic acid two Reactive cross-linking monomer with 2 or more reactive functional groups in allyl ester, butanediol diacrylate equimolecular.

Wherein, preferably above-mentioned from the viewpoint of it can be easily adjusted to the refractive index of nucleocapsid type rubber particle Core part is to include containing comprising (methyl) acrylate and aromatic ethenyl compound (especially butyl acrylate and benzene second Alkene) binary or ternary copolymer core part.

The glass transition temperature for constituting the polymer of above-mentioned core part is not particularly limited, preferably -100~10 DEG C, More preferably -80~-10 DEG C, further preferably -60~-20 DEG C.By making the glass transition temperature of above-mentioned polymer exist Above range, there are the tendencies that the resistance to cracking of solidfied material improves.It should be noted that constitute the polymer of above-mentioned core part Glass transition temperature is indicated using following calculated calculated values of Fox formulas (referring to Bull.Am.Phys.Soc., 1 (3) 123 (1956)).In following Fox formulas, Tg indicates the glass transition temperature (unit of the polymer of structure nucleation portion:K), W_iIt indicates The weight fraction of monomer i for the composition monomer total amount of the polymer of structure nucleation portion.In addition, Tg_iIndicate monomer i Homopolymer glass transition temperature (unit:K).Following Fox formulas indicate that the polymer for constituting core is monomer 1, monomer 2, and the formula in the case of the copolymer of monomer n.

1/Tg=W₁/Tg₁+W₂/Tg₂+....+W_n/Tg_n

The glass transition temperature of above-mentioned homopolymer can be used in the value described in various documents, for example, can be used Value described in " POLYMER HANDBOOK the 3rd edition " (John Wiley＆Sons, Inc. distribution).It should be noted that about Without those of recording in document, being surveyed by DSC methods for obtained from conventional method makes monomer polymerization homopolymer can be used The value of fixed glass transition temperature.

Above-mentioned core part can utilize usually adopted method to manufacture, for example, poly- using making above-mentioned monomer pass through lotion Legal method being polymerize etc. manufactures.In emulsion polymerization, the above-mentioned monomer for the whole amount that both can disposably feed intake And polymerize, it continually or intermittently can also add surplus after the part polymerization for making above-mentioned monomer and be gathered It closes, further, the polymerization using seed particles can also be used.

It should be noted that in the case where using the rubber particles without nucleocapsid as rubber particles (B), it can Use the rubber particles etc. for example only formed by above-mentioned core part.

The polymer for constituting the shell of nucleocapsid type rubber particle is preferably not of the same race with the polymer for constituting above-mentioned core part Polymer (with different monomers composition polymer).In addition, as described above, it is preferred to above-mentioned shell has hydroxyl and/or carboxylic Base is as the functional group that can be reacted with compounds with epoxy group such as cycloaliphatic epoxies (A).As a result, particularly, Can make with the cementability of the interface of cycloaliphatic epoxy (A) improve, so as to relative to make comprising have the shell Layer nucleocapsid type rubber particle hardening resin composition solidification made of solidfied material and play excellent resistance to cracking.Separately Outside, it is also prevented from the reduction of the glass transition temperature of solidfied material.

The polymer of above-mentioned shell is constituted preferably comprising (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) polymer of (methyl) acrylate as necessary monomer component such as butyl acrylate.For example, using butyl acrylate In the case of as (methyl) acrylate in above-mentioned core part, as the monomer component for the polymer for constituting shell, preferably Using for example：(methyl) acrylate other than butyl acrylate is (for example, (methyl) methyl acrylate, (methyl) acrylic acid second Ester, butyl methacrylate etc.).As the monomer component for optionally including other than (methyl) acrylate, it can be mentioned, for example：Benzene The aromatic ethenyl compounds such as ethylene, α-methylstyrene；Nitriles such as acrylonitrile, methacrylonitrile etc..In nucleocapsid type rubber grain Preferably also include in above-mentioned monomer while comprising (methyl) acrylate as the monomer component for constituting shell in son It is individually one or more kinds of, in particular, from the viewpoint that can be easily adjusted to the refractive index of nucleocapsid type rubber particle It sets out, preferably at least includes aromatic ethenyl compound.

Further, for constituting the polymer of above-mentioned shell, in order to be formed as can be with cycloaliphatic epoxy (A) hydroxyl and/or carboxyl for the functional group that compound with epoxy group is reacted such as, preferably comprise hydroxyl monomer (for example, (methyl) hydroxyalkyl acrylates such as (methyl) acrylic acid 2- hydroxy methacrylates etc.), carboxyl group-containing monomer is (for example, (methyl) propylene The alpha, beta-unsaturated acids such as acid；Alpha, beta-unsaturated acids acid anhydride such as maleic anhydride etc.) it is used as monomer component.

In the polymer for constituting above-mentioned shell, as monomer component, preferably while comprising (methyl) acrylate also Combination is comprising selected from one or more of above-mentioned monomer.That is, above-mentioned shell is preferably for example comprising (methyl) acrylic acid Ester/aromatic ethenyl compound/(methyl) hydroxyalkyl acrylates, (methyl) acrylate/aromatic vinyl close The shell of the terpolymers such as object/alpha, beta-unsaturated acid etc..

In addition, in the polymer for constituting above-mentioned shell, as other monomer components, in the same manner as core part, in addition to upper It states other than monomer, divinylbenzene, (methyl) allyl acrylate, ethylene glycol two (methyl) acrylate, horse can also be contained That there are 2 in diallyl phthalate, triallyl cyanurate, dially phthalate, butanediol diacrylate equimolecular The reactive cross-linking monomer of the above reactive functional groups.

The glass transition temperature for constituting the polymer of above-mentioned shell is not particularly limited, preferably 20~200 DEG C, more excellent It is selected as 40~180 DEG C, further preferably 60~160 DEG C.By make above-mentioned polymer glass transition temperature be 20 DEG C with On, there are the tendencies that the heat resistance of solidfied material and light resistance further increase.On the other hand, by making the glass of above-mentioned polymer Change transition temperature at 200 DEG C hereinafter, there are the tendencies that the resistance to cracking of the dispersibility of rubber particles (B) and solidfied material improves.It needs It is noted that the glass transition temperature for constituting the polymer of above-mentioned shell indicates to utilize the above-mentioned calculated calculating of Fox formulas Value, such as measurement can be carried out similarly with the glass transition temperature of the polymer of above-mentioned composition core.

Nucleocapsid type rubber particle can coat above-mentioned core part by using shell and obtain.It is above-mentioned as being coated using shell The method of core part, it can be mentioned, for example：By being applied using the surface of the core part obtained by the above method with caoutchouc elasticity Cloth constitutes the polymer of shell and the method that is coated；To be using the core part obtained by the above method with caoutchouc elasticity Dry ingredients, the method etc. being graft-polymerized as branch ingredient using constituting each ingredient of shell.

The average grain diameter of rubber particles (B) is not particularly limited, preferably 10~500nm, more preferably 20~400nm. In addition, the maximum particle diameter of rubber particles (B) is not particularly limited, preferably 50~1000nm, more preferably 100~800nm.It is logical Crossing makes average grain diameter be 500nm or less (or maximum particle diameter is made to be 1000nm or less), and there are the rubber particles (B) in solidfied material The tendency that dispersibility improves, resistance to cracking improves.On the other hand, (or make maximum particle diameter by making average grain diameter be 10nm or more For 50nm or more), there are the tendencies that the resistance to cracking of solidfied material improves.

The refractive index of rubber particles (B) is not particularly limited, and preferably 1.40~1.60, more preferably 1.42~1.58. In addition, the refractive index of rubber particles (B) and making the hardening resin composition (solidification of the invention for including the rubber particles (B) Property resin combination) solidification obtained from solidfied material specific refractivity preferably within ± 0.03.

The refractive index of rubber particles (B) can for example be found out as follows：Rubber particles (B) 1g is cast into mold, in 210 DEG C, 4MPa progress compression formings, obtain the tablet of thickness 1mm, the test film of 20mm × horizontal 6mm are indulged under gained flat plate cutting, In the state of making prism and the test film closely sealed using single bromination naphthalene as intermediate fluid, multi-wavelength Abbe refractometer is used Refractive index under 20 DEG C of (trade name " DR-M2 ", (strain) Atago systems) measurement, sodium D-line, thus finds out the refraction of rubber particles (B) Rate.

The refractive index of the solidfied material of the hardening resin composition of the present invention can for example be found out as follows：From using under The test film that the solidfied material that the method for being heating and curing described in the item of solidfied material obtains cuts vertical 20mm × horizontal 6mm × thickness 1mm is stated, In the state of making prism and the test film closely sealed using single bromination naphthalene as intermediate fluid, multi-wavelength Abbe refractometer is used Refractive index under 20 DEG C of (trade name " DR-M2 ", (strain) Atago systems) measurement, sodium D-line, thus finds out the refractive index of solidfied material.

The content (use level) of rubber particles (B) in the hardening resin composition of the present invention is not particularly limited, but Relative to hardening resin composition (100 weight %), preferably 0.01~20 weight %, more preferably 0.05~15 weight Measure %, further preferably 0.1~10 weight %.By making the content of rubber particles (B) in above range, there are solidfied materials Resistance to cracking raising, heat resistance and the more excellent tendency of light resistance.

The content (use level) of rubber particles (B) in the hardening resin composition of the present invention is not particularly limited, but Relative to 100 parts by weight of total amount for the compound with epoxy group for including in hardening resin composition, preferably 0.5~30 Parts by weight, more preferably 1~20 parts by weight.By making the content of rubber particles (B) in above range, resistance to there are solidfied material opens Fragility raising, heat resistance and the more excellent tendency of light resistance.

[white pigment (C)]

The white pigment (C) of the neccessary composition of hardening resin composition as the present invention mainly has to solidfied material The effect that (reflector) assigns high light reflectivity and its linear expansion coefficient is made to reduce.As white pigment (C), can be used Known or usual white pigment, is not particularly limited, it can be mentioned, for example：Glass, clay, mica, talcum, kaolinite (kaolinite Soil), galapectite, zeolite, Emathlite, atlapulgite, boehmite, pseudobochmite, inorganic oxide, metal salt is [for example, alkaline earth Metal salt etc.] etc. inorganic white pigments；Styrene resin, benzoguanamine resinoid, urea-formaldehyde resinoid, melamine-first The organic white pigments such as the resin pigments such as air aldehyde resin, amide resinoid (plastic pigment etc.)；With hollow structure (balloon structure (balloon structure)) hollow-particle etc..

As white pigment (C), in order to improve reflector reflectivity, it is preferable to use high refractive index white pigment, it is excellent The white pigment that choosing such as refractive index is 1.5 or more.It should be noted that the white pigment with hollow-particle structure is due to interior Portion's (core) includes that gas, the surface reflectivity of low-refraction are very big, therefore shell parts can also be less than 1.5 material by refractive index Material is constituted.It should be noted that about inorganic filler (D) is being also belonged in exemplary substance as white pigment (C) Those, regard refractive index as inorganic filler (D) as white pigment (C), by refractive index for 1.5 or more less than 1.5.

As above-mentioned inorganic oxide, it can be mentioned, for example：Aluminium oxide (alumina), magnesia, antimony oxide, titanium oxide [for example, Titanium Dioxide Rutile Top grade, anatase-type titanium oxide, brookite type titanium oxide etc.], zirconium oxide, zinc oxide etc..In addition, as above-mentioned Alkali salt, it can be mentioned, for example：Magnesium carbonate, calcium carbonate, barium carbonate, magnesium silicate, calcium silicates, magnesium hydroxide, magnesium phosphate, phosphoric acid Hydrogen magnesium, magnesium sulfate, calcium sulfate, barium sulfate etc..In addition, as the metal salt other than alkali salt, it can be mentioned, for example：Silicic acid Aluminium, aluminium hydroxide, zinc sulphide etc..

As above-mentioned hollow-particle, it is not particularly limited, it can be mentioned, for example：Unorganic glass is [for example, water soda glass, silicon Sour lead glass, sodium borosilicate glass, quartz etc.], by the metal oxides such as silica, aluminium oxide, calcium carbonate, barium carbonate, carbon The inorganic hollow particle (also including the natural goods such as Silas balloon) that the inorganic matters such as the metal salts such as sour nickel, calcium silicates are constituted；By Styrene resin, acrylic resin, the resin of organic silicon, acrylicstyrene resinoid, vinyl chloride resin, partially Vinyl chloride resin, amide resinoid, polyurethane based resin, phenolic resinoid, styrene-conjugated diene resinoid, acrylic acid- The organic matters such as the polymer such as conjugated diene resinoid, olefine kind resin (cross-linking agent for also including these polymer) are constituted organic Hollow-particle；The inorganic-organic hollow-particle etc. being made of the mixing material of inorganic matter and organic matter.On it should be noted that Stating hollow-particle can be made of homogenous material, can also be made of two or more materials.In addition, in above-mentioned hollow-particle Empty portion (inner space of hollow-particle) can be vacuum state, can also be full of by medium, but especially from raising reflectivity From the perspective of, preferably it is refracted the hollow-particle that the low medium of rate (for example, the inactive gas such as nitrogen, argon, air etc.) is full of.

It should be noted that white pigment (C) can also be to be carried out known or usual surface treatment [for example, profit The surface carried out with surface conditioning agents such as metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyalcohol, siloxanes Processing etc.] made of material.By being surface-treated as implementation, can make sometimes with it is other in hardening resin composition Compatibility, the dispersibility of ingredient improve.

Wherein, as white pigment (C), from availability, heat resistance, sunproof viewpoint and solidfied material (reflector) High reflectance and climbing relative to the light reflective of additive amount from the perspective of, preferably inorganic oxide, it is inorganic in Empty particle, more preferably aluminium oxide, magnesia, antimony oxide, titanium oxide, zirconium oxide, zinc oxide, barium sulfate, inorganic hollow particle, Further preferably titanium oxide, zirconium oxide, zinc oxide, barium sulfate.In particular, as white pigment (C), from higher folding It penetrates from the viewpoint of rate, preferably titanium oxide.

The shape of white pigment (C) is not particularly limited, and it can be mentioned, for example spherical, broken shape, threadiness, needle-shaped, scales Shape etc..Wherein, from the viewpoint of dispersibility, preferably spherical titanium oxide, particularly preferably just spherical titanium oxide (example Such as, aspect ratio is 1.2 spherical titanium oxide below).

The medium particle diameter of white pigment (C) is not particularly limited, but from the light reflective for improving solidfied material (reflector) Viewpoint consideration, preferably 0.1~50 μm.In particular, in the case where using titanium oxide as white pigment (C), the titanium oxide Medium particle diameter be not particularly limited, but preferably 0.1~50 μm, more preferably 0.1~30 μm, further preferably 0.1~ 20 μm, particularly preferably 0.1~10 μm, most preferably 0.1~5 μm.On the other hand, empty particle in use is (especially inorganic Hollow-particle) as in the case of white pigment (C), the medium particle diameter of the hollow-particle is not particularly limited, but preferably 0.1 ~50 μm, more preferably 0.1~30 μm.It should be noted that above-mentioned medium particle diameter refers to being surveyed using laser diffraction/scattering method Grain size (median particle diameter) when aggregate-value is 50% in fixed size distribution.

In the hardening resin composition of the present invention, white pigment (C) can be used alone, can also be by two kinds Combination of the above uses.In addition, white pigment (C) can both be manufactured by known or customary way, can also use for example Trade name " SR-1 ", " R-42 ", " R-45M ", " R-650 ", " R-32 ", " R-5N ", " GTR-100 ", " R-62N ", " R-7E ", " R-44 ", " R-3L ", " R-11P ", " R-21 ", " R-25 ", " TCR-52 ", " R-310 ", " D-918 ", " FTR-700 " (above by Sakai chemical industry (strain) make), trade name " Tipaque CR-50 ", " CR-50-2 ", " CR-60 ", " CR-60-2 ", " CR-63 ", " CR-80 ", " CR-90 ", " CR-90-2 ", " CR-93 ", " CR-95 ", " CR-97 " (industry (strain) system is originated in by stone above), commodity Name " JR-301 ", " JR-403 ", " JR-405 ", " JR-600A ", " JR-605 ", " JR-600E ", " JR-603 ", " JR-805 ", " JR-806 ", " JR-701 ", " JRNC ", " JR-800 ", " JR " (being made above by Teika (strain)), trade name " TR-600 ", " TR- 700 ", " TR-750 ", " TR-840 ", " TR-900 " (being made above by Fuji's Ti industry (strain)), trade name " KR-310 ", " KR- 380”、“KR-380N”、“ST-410WB”、“ST-455”、“ST-455WB”、“ST-457SA”、“ST-457EC”、“ST- The Titanium Dioxide Rutile Top grades such as 485SA15 ", " ST-486SA ", " ST-495M " (being made above by Ti industry (strain))；Trade name " A- 110 ", " TCA-123E ", " A-190 ", " A-197 ", " SA-1 ", " SA-1L ", " SSP series ", " CSB series " are (above by Sakai Learn industrial (strain) system), trade name " JA-1 ", " JA-C ", " JA-3 " (being made above by Teika (strain)), trade name " KA-10 ", " KA-15 ", " KA-20 ", " STT-65C-S ", " STT-30EHJ " (being made above by Ti industry (strain)), trade name " DCF-T- 17007 ", the anatases such as " DCF-T-17008 ", " DCF-T-17050 " (being made above by Resino Color Industry (strain)) The commercially available products such as type titanium oxide.

Wherein, as white pigment (C), the sight especially from the raising of the light reflective and heat resistance of solidfied material (reflector) Point consider, preferably trade name " R-62N ", " CR-60 ", " DCF-T-17007 ", " DCF-T-17008 ", " DCF-T-17050 ", Those of " FTR-700 ".

The content (use level) of white pigment (C) in the hardening resin composition of the present invention is not particularly limited, but Relative to hardening resin composition (100 weight %), preferably 0.1~50 weight %, more preferably 1~40 weight %, into One step is preferably 5~35 weight %.By making the content of white pigment (C) be 0.1 weight % or more, there are solidfied material (reflections Body) the tendency that further increases of light reflective.Additionally, there are the tendencies that heat resistance and light resistance further increase.Another party Face, by making the content of white pigment (C) be 60 weight % hereinafter, there are the mouldabilities of solidfied material (reflector) to improve, more Tendency suitable for batch production.

The content (use level) of white pigment (C) in the hardening resin composition of the present invention is not particularly limited, but Relative to 100 parts by weight of total amount for the compound with epoxy group for including in hardening resin composition, preferably 10~600 Parts by weight, more preferably 30~500 parts by weight, further preferably 30~400 parts by weight.By making containing for white pigment (C) Amount is 10 parts by weight or more, and there are the tendencies that the light reflective of solidfied material (reflector) further increases.Additionally, there are heat resistances And the tendency that light resistance further increases.On the other hand, by make white pigment (C) content be 600 parts by weight hereinafter, in the presence of The mouldability of solidfied material (reflector) improves, is more suitable for the tendency of batch production.

In the case that the hardening resin composition of the present invention contains titanium oxide, relative to white pigment (C) and inorganic fill out The ratio for filling the titanium oxide of the total amount (100 weight %) of agent (D) is not particularly limited, but from the heat resistance of solidfied material (reflector) From the viewpoint of the balance of light reflective, preferably 5~70 weight %, more preferably 10~60 weight %.By making oxidation The ratio of titanium is 5 weight % or more, and there are the tendencies that the light reflective of solidfied material (reflector) further increases.Additionally, there are The tendency that heat resistance and light resistance further increase.On the other hand, by make titanium oxide ratio be 70 weight % hereinafter, in the presence of The mouldability of solidfied material (reflector) improves, is more suitable for the tendency of batch production.

[inorganic filler (D)]

In the hardening resin composition of the present invention, with being different from white pigment (C), including inorganic filler (D) conduct Neccessary composition.Inorganic filler (D) is mainly that solidfied material (reflector) assigns excellent heat resistance and light resistance (in particular, excellent Different heat resistance).In addition, having the function of making the linear expansion coefficient of solidfied material (reflector) to reduce.In addition, being filled out according to inorganic The type for filling agent (D) is different, it is also possible to excellent light reflective is assigned for solidfied material (reflector).

As inorganic filler (D), known or usual inorganic filler can be used, be not particularly limited, example can be enumerated Such as：Silica, alumina, zircon, calcium silicates, calcium phosphate, calcium carbonate, magnesium carbonate, silicon carbide, silicon nitride, boron nitride, hydroxide Aluminium, iron oxide, zinc oxide, zirconium oxide, magnesia, titanium oxide, aluminium oxide, calcium sulfate, barium sulfate, forsterite, lardite, point are brilliant The powders such as stone, clay, kaolin, dolomite, hydroxyapatite, nepheline syenite, cristobalite, wollastonite, diatomite, talcum, Or their formed body (for example, by pearl made of spheroidization etc.) etc..In addition, as inorganic filler (D), can also enumerate Material etc. made of known or usual surface treatment is implemented to above-mentioned inorganic filler.Wherein, as inorganic filler (D), from the viewpoint of the heat resistance, light resistance and mobility of solidfied material (reflector), preferably silica, aluminium oxide, Silicon nitride, aluminium nitride, boron nitride.

It as silica, is not particularly limited, such as fused silica, crystalline silica, high-purity can be used Known in synthetic silica etc. or usual silica.It should be noted that as silica, can also use implement Known or usual surface treatment is [for example, utilize metal oxide, silane coupling agent, titanium coupling agent, organic acid, polyalcohol, silicon The surface conditioning agents such as oxygen alkane and the surface treatment etc. carried out] silica.

The shape of silica is not particularly limited, and it can be mentioned, for example powder, spherical, broken shape, threadiness, needle-shaped, squamas Sheet etc..Wherein, from the viewpoint of dispersibility, preferably spherical silica, particularly preferably just spherical titanium dioxide Silicon (for example, aspect ratio is 1.2 spherical silica below).

The medium particle diameter of silica is not particularly limited, but the viewpoint of the light reflective from raising solidfied material (reflector) Consider, preferably 0.1~50 μm, more preferably 0.1~30 μm.It should be noted that above-mentioned medium particle diameter refers to swashing in utilization Grain size (median particle diameter) when aggregate-value is 50% in the size distribution of optical diffraction/scattering method.

It should be noted that in the hardening resin composition of the present invention, inorganic filler (D) can be used alone one Kind, it can also be used in combination of two or more.In addition, inorganic filler (D) can both utilize known or usual manufacturing method Manufacture, can also use such as trade name " FB-910 ", " FB-940 ", " FB-950 ", " FB-105 ", " FB-105FD ", " FB- 5D”、“FB-8S”、“FB-7SDC”、“FB-5SDC”、“FB-3SDC”、“FB-9FDC”、“FB-7FDC”、“FB-5FDC”、“FB- The FB such as 970FD ", " FB-975FD ", " FB-950FD ", " FB-40RFD " series, trade name " DAW-03DC ", " DAW-0525 ", The series such as " DAW-1025 " DAW, trade name " SGP " (being made above by Denka (strain)), trade name " HF-05 " ((strain) Tokuyama System), trade name " 10 μm of SE-CC5 " ((strain) Admatechs systems), trade name " MSR-2212 ", " MSR-25 " (above by (strain) The gloomy system of dragon), trade name " HS-105 ", " HS-106 ", the commercially available products such as " HS-107 " (above by Micron corporations).

The content (use level) of inorganic filler (D) in the hardening resin composition of the present invention is not particularly limited, But relative to hardening resin composition (100 weight %), preferably 10~90 weight %, more preferably 13~75 weight %, Further preferably 15~70 weight %, further preferably 20~70 weight %.Content by making inorganic filler (D) is 10 weight % or more, there are the tendencies that the heat resistance of solidfied material and light resistance (in particular, excellent heat resistance) further increase. Additionally, there are the linear expansion coefficients of solidfied material (reflector) to reduce, is not susceptible in the photosemiconductor for having used the reflector The tendency of a problem that warpage of lead frame on element mounting substrate.On the other hand, by making inorganic filler (D) Content is 90 weight % hereinafter, there are the mouldabilities of solidfied material (reflector) to improve, is more suitable for the tendency of batch production.

The content (use level) of inorganic filler (D) in the hardening resin composition of the present invention is not particularly limited, But relative to 100 parts by weight of total amount for the compound with epoxy group for including in hardening resin composition, preferably 10~ 1500 parts by weight, more preferably 50~1200 parts by weight, further preferably 100~1000 parts by weight.By making inorganic fill The content of agent (D) is 10 parts by weight or more, and there are the heat resistance of solidfied material and lights resistance (in particular, excellent heat resistance) into one Walk the tendency improved.Additionally, there are the linear expansion coefficients of solidfied material (reflector) to reduce, is not susceptible to using the reflection The tendency of a problem that warpage of lead frame on the optical semiconductor board for mounting electronic of body.On the other hand, by making nothing The content of machine filler (D) is 1500 parts by weight hereinafter, there are the mouldabilities of solidfied material (reflector) to improve, is more suitable for batch The tendency of production.

The maximum particle diameter of white pigment (C) and inorganic filler (D) in the hardening resin composition of the present invention does not have Particular determination, but preferably 200 μm or less, more preferably 185 μm or less, further preferably 175 μm or less, be particularly preferably 150 μm or less.When above-mentioned maximum particle diameter is 200 μm or less, and uses maximum particle diameter to be more than 200 μm of white pigment or inorganic fill out The case where filling agent is compared, and there are the heat resistance of solidfied material, light resistance and resistance to cracking (especially excellent heat resistance) are more excellent Different tendency.In addition, by using the small white pigment of maximum particle diameter (C) and inorganic filler (D), it can be by their content Increase, thus there are the tendencies that the light reflective of solidfied material, heat resistance and light resistance further improve.Above-mentioned maximum particle diameter Lower limit is, for example, 0.01 μm or more.It should be noted that above-mentioned maximum particle diameter be the present invention hardening resin composition in wrap Total maximum particle diameter of the white pigment (C) and inorganic filler (D) that contain.Above-mentioned maximum particle diameter refer to using laser diffraction/ Maximum grain size in the size distribution of scattering method.

[curing agent (E)]

The present invention hardening resin composition in curing agent (E) be have by with cycloaliphatic epoxy (A) Make the compound of the cured effect of hardening resin composition Deng the compound reaction with epoxy group.As curing agent (E), Known or usual hardener for epoxy resin can be used, be not particularly limited, it can be mentioned, for example：(anhydride cures anhydride Agent), amine (amine curing agent), polyamide, imidazoles (imidazole curing agent), polysulfide alcohols (polysulfide alcohols cure Agent), phenols (phenols curing agent), polycarboxylic acid, dicyandiamide class, organic hydrazides etc..

As the anhydride (acid anhydride type curing agent) as curing agent (E), known or usual anhydride solidification can be used Agent is not particularly limited, it can be mentioned, for example：Methyl tetrahydrophthalic anhydride (4- methyl tetrahydrophthalic anhydrides, 3- methyl Tetrabydrophthalic anhydride etc.), (4- methylhexahydrophthalic anhydrides, 3- methyl hexahydro are adjacent for methylhexahydrophthalic anhydride Phthalate anhydride etc.), dodecenyl succinic anhydride, methylendomethylene tetrabydrophthalic anhydride, phthalic anhydride, horse Come acid anhydrides, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic dianhydride, inclined benzene Three acid anhydrides, benzophenone tetracarboxylic acid anhydride, carbic anhydride, methylnadic anhydride, hydrogenating methyl carbic anhydride, 4- (4- first Base -3- pentenyls) tetrabydrophthalic anhydride, succinic anhydride, adipic anhydride, sebacic anhydride, dodecanedioic acid acid anhydride, methyl cyclohexane Alkene tetracarboxylic acid anhydride, vinyl ether-maleic acid copolymer, ring-alkylated styrenes-copolymer-maleic anhydride etc..Wherein, from can have Effect ground prepares the viewpoint of uniform hardening resin composition, is easy to mix with cycloaliphatic epoxy (A) and forms 25 DEG C Down be liquid mixture (curing agent composition) from the perspective of, at preferably 25 DEG C for liquid acid anhydrides [for example, methyl four Hydrogen phthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylene tetrahydrochysene neighbour benzene two Formic anhydride etc.].On the other hand, about the acid anhydrides at 25 DEG C being solid-like, for example, by making it dissolve at 25 DEG C as liquid Acid anhydrides and the mixture that liquid is made, operability of the operation as the curing agent (E) in hardening resin composition of the invention The tendency of raising.As acid anhydride type curing agent, from the viewpoint of the heat resistance of solidfied material, light reflective, preferably saturation is single The acid anhydrides (be also included on ring and be bonded with those of substituent groups such as alkyl) of cyclic hydrocarbon dicarboxylic acids.

As the amine (amine curing agent) as curing agent (E), known or usual amine curing agent can be used, do not have Particular determination, it can be mentioned, for example：Ethylenediamine, diethylenetriamines, trien, tetren, dipropylene two The aliphatic polyamines such as amine, diethyl amino propyl amine, polytrimethylene triamine；Alkene diamines, isophorone diamine, bis- (4- amino- 3- methyldicyclohexyls) methane, diamino-dicyclohexyl methane, bis- (amino methyl) hexamethylenes, N- aminoethylpiperazines, 3,9- The ester ring types polyamines such as four oxaspiro [5,5] hendecanes of bis- (3- aminopropyls) -3,4,8,10-；M-phenylene diamine (MPD), p-phenylenediamine, first Benzene -2,4- diamines, Toluene-2,4-diisocyanate, 6- diamines, mesitylene -2,4- diamines, 3,5- diethyltoluene -2,4- diamines, 3,5- diethyls Base Toluene-2,4-diisocyanate, the monokaryons such as 6- diamines polyamines, benzidine, 4,4- diaminodiphenyl-methanes, 2,5- naphthylenediamines, 2,6- naphthylenediamines Equal aromatic polyamines etc..

As the phenols (phenols curing agent) as curing agent (E), known or usual phenols curing agent can be used, do not have Particular determination, it can be mentioned, for example：Novolak phenolics, phenolic varnish type cresol novolac resin, paraxylene are modified phenol The aralkyl resins such as urea formaldehyde, paraxylene/meta-xylene phenol-formaldehyde resin modified, terpene modified phenolic resin, bicyclopentadiene Phenol-formaldehyde resin modified, trisphenol propane etc..

As the polyamide as curing agent (E), it can be mentioned, for example：Intramolecular has in primary amino group and secondary amino group The polyamide etc. of any one or both.

As the imidazoles (imidazole curing agent) as curing agent (E), known or usual imidazoles solidification can be used Agent is not particularly limited, it can be mentioned, for example：2-methylimidazole, 2-ethyl-4-methylimidazole, 2- undecyl imidazoles, 2- 17 Alkyl imidazole, 2- phenylimidazoles, 1 benzyl 2 methyl imidazole, 1- cyano ethyls -2-methylimidazole, 1- cyano ethyl -2- second Base -4-methylimidazole, 1- cyano ethyl -2- undecyl imidazoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acids Salt, 1- cyano ethyl -2- phenylimidazole trimellitic acids salt, 2-methylimidazole isocyanurate, 2- phenylimidazole isocyanides Urea hydrochlorate, 2,4- diamino -6- [2-methylimidazole base-(1)]-ethyl-s-triazine, 2,4- diamino -6- [2- ethyl -4- first Base imidazole radicals-(1)]-ethyl-s-triazine etc..

As the polysulfide alcohols (polysulfide alcohols curing agent) as curing agent (E), it can be mentioned, for example：The polymercaptan of liquid, Thio resin etc..

As the polycarboxylic acid as curing agent (E), it can be mentioned, for example：Adipic acid, decanedioic acid, terephthalic acid (TPA), inclined benzene Three acid, carboxylic polyester etc..

Wherein, as curing agent (E), from the viewpoint of the heat resistance, light resistance, light reflective of solidfied material, preferred acid Anhydride (acid anhydride type curing agent).It should be noted that in the hardening resin composition of the present invention, curing agent (E) can be single Solely using one kind, can also be used in combination of two or more.It should be noted that curing agent both can be known in or usual Method manufactures, and can also use such as trade name " RIKACID MH-700 ", " RIKACID MH-700F ", " RIKACID MH- 700G ", " RIKACID TH ", " RIKACID HH ", " RIKACID HNA-100 " (being made above by new Japan Chemical (strain))；Quotient The name of an article " HN-5500 " (Hitachi Chemical Industries (Ltd.) system)；Trade name " H-TMAn-S ", " H-TMAn " are (above by Mitsubishi's gas Learn (strain) system)；The commercially available products such as trade name " YH1120 " (Mitsubishi Chemical's (strain) system).

In the case that the hardening resin composition of the present invention contains curing agent (E), the content (use level) of curing agent (E) It is not particularly limited, but relative to hardening resin composition (100 weight %), preferably 1~40 weight %, more preferably 3 ~35 weight %, further preferably 5~30 weight %.Content by making curing agent (E) is 1 weight % or more, is existed solid Changing becomes the tendency that more abundant, solidfied material resistance to cracking improves.On the other hand, by making the content of curing agent (E) be 40 Weight % hereinafter, in the presence of be easy to get coloring further suppressed, the tendency for the solidfied material (reflector) that form and aspect are excellent.

In the case that the hardening resin composition of the present invention contains curing agent (E), the content (use level) of curing agent (E) It is not particularly limited, but relative to 100 weight of total amount for the compound with epoxy group for including in hardening resin composition Part, preferably 40~200 parts by weight, more preferably 50~150 parts by weight.More specifically, anhydride is being used to be used as solidification In the case of agent (E), all changes with epoxy group preferably to include in the hardening resin composition relative to the present invention Close the ratio use that every 1 equivalent of epoxy group in object reaches 0.5~1.5 equivalent.By making the content of curing agent (E) be 40 weight Part or more, there is solidification becomes the tendency that more abundant, solidfied material resistance to cracking improves.On the other hand, by making curing agent (E) content is 200 parts by weight hereinafter, in the presence of the solidfied material (reflection that coloring is further suppressed, form and aspect are excellent is easy to get Body) tendency.

[curing accelerator (F)]

The hardening resin composition of the present invention can also include curing accelerator (F).Curing accelerator (F) is that have to promote Into the compound with epoxy group for including in the hardening resin composition of the present invention (for example, cycloaliphatic epoxy (A), isocyanuric acid derivative (H) and silicone derivative (I)) reaction speed when being reacted with curing agent such as curing agent (E) The compound of function.As curing accelerator (F), known or usual curing accelerator can be used, it can be mentioned, for example：1,8- bis- Azabicyclo [5.4.0] endecatylene -7 (DBU) or its salt are (for example, phenates, caprylate, tosilate, formates, four Phenylboronate etc.)；1,5- diazabicyclo [4.3.0] nonene -5 (DBN) or its salt (for example, phenates, caprylate, to toluene Sulfonate, formates, tetraphenyl borate salts etc.)；Benzyldimethylamine, 2,4,2,4,6- tri- (dimethylaminomethyl) phenol, N, N- The tertiary amines such as dimethylcyclohexylam,ne；The imidazoles such as 2-ethyl-4-methylimidazole, 1- cyano ethyls -2-ethyl-4-methylimidazole；Phosphorus The phosphines such as acid esters, triphenylphosphine；Tetraphenylphosphoniphenolate four (p-methylphenyl) borate Deng phosphonium compounds；Zinc octoate, tin octoate etc. are organic Metal salt；Metallo-chelate etc..

In the hardening resin composition of the present invention, curing accelerator (F) can be used alone, can also be by two kinds Combination of the above uses.

In addition, curing accelerator (F) can both be manufactured by known or customary way, such as commodity can also be used Name " U-CAT SA 506 ", " U-CAT SA 102 ", " U-CAT 5003 ", " U-CAT 18X ", " 12XD " (exploitation product) (more than It is made by San-Apro (strain))；Trade name " TPP-K ", " TPP-MK " (being made above by the emerging chemical industry (strain) in north)；Trade name " PX- The commercially available products such as 4ET " (Japan Chemical Industry (strain) system).

In the case that the hardening resin composition of the present invention contains curing accelerator (F), the content of curing accelerator (F) (use level) is not particularly limited, but relative to hardening resin composition (100 weight %), preferably 0.0001~5 weight Measure %, more preferably 0.001~1 weight %.Content by making curing accelerator (F) is 0.0001 weight % or more, is existed The tendency that curing reaction can be made to be more effectively carried out.On the other hand, by making the content of curing accelerator (F) be 5 weight % Hereinafter, the keeping quality there are hardening resin composition further increases, or be easy to get coloring further suppressed, form and aspect The tendency of excellent solidfied material (reflector).

In the case that the hardening resin composition of the present invention contains curing accelerator (F), the content of curing accelerator (F) (use level) is not particularly limited, but relative to the total amount for the compound with epoxy group for including in hardening resin composition 100 parts by weight, preferably 0.05~15 parts by weight, more preferably 0.1~12 parts by weight, further preferably 0.2~10 weight Part, particularly preferably 0.25~8 parts by weight.Content by making curing accelerator is 0.05 parts by weight or more, and existing can make The tendency that curing reaction is more effectively carried out.On the other hand, by make curing accelerator content be 15 parts by weight hereinafter, in the presence of The keeping quality of hardening resin composition further increases, or is easy to get that coloring, which is further suppressed, form and aspect are excellent consolidates The tendency of compound (reflector).

[curing catalysts (G)]

Curing catalysts (G) in the hardening resin composition of the present invention are that have by causing and/or promoting alicyclic ring The curing reaction (polymerisation) of the cationically polymerizables compounds such as formula epoxide (A) and so that hardening resin composition is consolidated The compound of the effect of change.As curing catalysts (G), it is not particularly limited, it can be mentioned, for example：By implementing illumination or heating Processing etc. and generate that cation kind, causing the cationic polymerization initiators of polymerization, (light cationic polymerization initiator, heat cation are poly- Close initiator etc.), lewis acid-amine complex, Bronsted Barbiturates, imidazoles etc..

As the light cationic polymerization initiator as curing catalysts (G), it can be mentioned, for example：Hexafluoro antimonate, five fluorine Hydroxyl stibate, hexafluorophosphate, hexafluoro arsenate etc., more specifically, it can be mentioned, for example：Triaryl matte hexafluorophosphate The sulfonium salts such as (for example, to phenylthiophenyl diphenyl sulfonium hexafluorophosphate etc.), triaryl matte hexafluoro antimonate are (in particular, three Aryl sulfonium salt)；Diaryl iodonium hexafluorophosphate, Diaryl iodonium hexafluoro antimonate, bis- (dodecylphenyl) iodine four (five Fluorophenyl) salt compounded of iodine such as borate, iodine [4- (4- aminomethyl phenyl -2- methyl-propyls) phenyl] hexafluorophosphate；Si Fu Phosphonium six Fluorophosphate Deng phosphonium salts；Pyridiniujms such as N- hexyl pyridinium tetrafluoroborate salt etc..In addition, causing as light cationic polymerization Agent will also be preferred for example：Trade name " UVACURE1590 " (Daicel-Cytec (strain) systems)；Trade name " CD-1010 ", " CD-1011 ", " CD-1012 " (above by Sartomer Americas systems)；Trade name " Irgacure 264 " (BASF AG System)；The commercially available products such as trade name " CIT-1682 " (Japanese Cao makes up to (strain)).

As the hot cationic polymerization as curing catalysts (G), it can be mentioned, for example：Aryl diazonium salts, aryl Salt compounded of iodine, aryl sulfonium salt, aromatic hydrocarbons-ionic complex etc., preferable commodity in use name " PP-33 ", " CP-66 ", " CP-77 " (with Upper (strain) ADEKA systems)；Trade name " FC-509 " (3M systems)；Trade name " UVE1014 " (G.E. systems)；Trade name " San Aid SI-60L”、“San Aid SI-80L”、“San Aid SI-100L”、“San Aid SI-110L”、“San Aid SI- 150L " (is made by three new chemical industry (strain)) above；The commercially available products such as trade name " CG-24-61 " (BASF AG's system).Further, As hot cationic polymerization, can also enumerate：The metals such as aluminium, titanium and acetoacetate or the chelate compound and three of diones The chelate compound of compound that the silanols such as phenyl silane alcohol are formed or the metals such as aluminium, titanium and acetoacetate or diones and The compound etc. that the phenols such as bisphenol S are formed.

As lewis acid-amine complex as curing catalysts (G), known or usual lewis acid-can be used Amine complex class curing catalysts, are not particularly limited, it can be mentioned, for example：BF₃N-hexylamine, BF₃Mono aminoethane, BF₃Benzylamine, BF₃Diethylamine, BF₃Piperidines, BF₃Triethylamine, BF₃Aniline, BF₄N-hexylamine, BF₄Mono aminoethane, BF₄Benzylamine, BF₄Diethyl Amine, BF₄Piperidines, BF₄Triethylamine, BF₄Aniline, PF₅Ethamine, PF₅Isopropylamine, PF₅Butylamine, PF₅Lauryl amine, PF₅Benzyl Amine, AsF₅Lauryl amine etc..

As the Bronsted Barbiturates as curing catalysts (G), known or usual Bronsted can be used Barbiturates is not particularly limited, it can be mentioned, for example：Aliphatic sulfonium salt, aromatic series sulfonium salt, salt compounded of iodine, phosphonium salts etc..

As the imidazoles as curing catalysts (G), known or usual imidazoles can be used, be not particularly limited, It can be mentioned, for example：2-methylimidazole, 2-ethyl-4-methylimidazole, 2- undecyl imidazoles, 2- heptadecyl imidazoles, 2- phenyl Imidazoles, 1 benzyl 2 methyl imidazole, 1- cyano ethyls -2-methylimidazole, 1- cyano ethyls -2-ethyl-4-methylimidazole, 1- Cyano ethyl -2- undecyl imidazoles, 1- cyano ethyl -2- undecyl imidazole trimellitic acids salt, 1- cyano ethyl -2- benzene Base imidazoles trimellitic acid salt, 2-methylimidazole isocyanurate, 2- phenylimidazoles isocyanurate, 2,4- diamino- 6- [2-methylimidazole base-(1)]-ethyl-s-triazine, 2,4- diamino -6- [2-ethyl-4-methylimidazole base-(1)]-ethyl - S-triazine etc..

In the hardening resin composition of the present invention, curing catalysts (G) can be used alone, can also be by two Kind combination of the above uses.It should be noted that as described above, as curing catalysts (G), commercially available product can also be used.

In the case that the hardening resin composition of the present invention contains curing catalysts (G), the content of curing catalysts (G) (use level) is not particularly limited, but relative to hardening resin composition (100 weight %), preferably 0.0001~5 weight Measure %, more preferably 0.001~1 weight %.By within the above range use curing catalysts (G), can obtain heat resistance, The solidfied material of excellent in light-resistance.

In the case that the hardening resin composition of the present invention contains curing catalysts (G), curable resin of the invention The content (use level) of curing catalysts (G) in composition is not particularly limited, but relative in hardening resin composition Including the compound with epoxy group 100 parts by weight of total amount, preferably 0.0001~15 parts by weight, more preferably 0.01~ 12 parts by weight, further preferably 0.05~10 parts by weight, particularly preferably 0.05~8 parts by weight.By making curing catalysts (G) within the above range, can be obtained heat resistance, excellent in light-resistance solidfied material.

[intramolecular has the isocyanuric acid derivative (H) of 1 or more oxirane ring]

The isocyanuric acid derivative (H) of the neccessary composition of hardening resin composition as the present invention is isocyanuric acid Derivative is the intramolecular at least compound with 1 or more oxirane ring.By the curable resin combination for making the present invention Object includes isocyanuric acid derivative (H), and the light reflective of solidfied material, heat resistance, light resistance improve, and by make its with it is aftermentioned Silicone derivative (I) while included in hardening resin composition, the light reflective of solidfied material, heat resistance, light resistance into One step improves.The number of oxirane ring possessed by the intramolecular of isocyanuric acid derivative (H) is 1 or more, is not had Particular determination, but preferably 1~6, more preferably 1~3.

As isocyanuric acid derivative (H), it can be mentioned, for example following formula (III) compounds represented.

[chemical formula 10]

In formula (III), R⁴~R⁶It is identical or different, indicate hydrogen atom or monovalent organic group.Also, R⁴~R⁶In extremely Few one is the monovalent organic group containing epoxy group.As above-mentioned monovalent organic group, it can be mentioned, for example：The aliphatic of monovalence Alkyl (for example, alkyl, alkenyl etc.)；The aromatic hydrocarbyl (for example, aryl etc.) of monovalence；The hetero ring type base of monovalence；By aliphatic 2 or more the univalent perssads etc. for being bonded and being formed in alkyl, alicyclic type hydrocarbon and aromatic hydrocarbyl.It should be noted that one Valence organic group can also have substituent group (for example, the substituent groups such as hydroxyl, carboxyl, halogen atom).As one containing epoxy group Valence organic group, it can be mentioned, for example：Epoxy group, glycidyl, 2- methylglycidyls, epoxycyclohexyl etc. it is aftermentioned containing The monovalent organic group etc. of epoxy group.

In particular it is preferred that the R in formula (III)⁴~R⁶It is group or following shown in following formula (IIIa) identical or differently Group and R shown in formula (IIIb)⁴~R⁶At least one of for group shown in formula (IIIa).

[chemical formula 11]

[chemical formula 12]

R in above-mentioned formula (IIIa) and formula (IIIb)⁷And R⁸It is identical or different, indicate hydrogen atom or carbon atom number 1~8 Alkyl.As the alkyl of carbon atom number 1~8, it can be mentioned, for example：Methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, Zhong Ding The alkyl of the straight or brancheds such as base, amyl, hexyl, heptyl, octyl.Wherein, preferably methyl, ethyl, propyl, isopropyl etc. The alkyl of the straight or branched of carbon atom number 1~3.R in particularly preferred formula (IIIa) and formula (IIIb)⁷And R⁸For hydrogen atom.

More specifically, as above-mentioned isocyanuric acid derivative (H), can enumerate following formula (III-1) compound represented, Following formula (III-2) compound represented, following formula (III-3) compound represented etc..

[chemical formula 13]

[chemical formula 14]

[chemical formula 15]

In above-mentioned formula (III-1)~(III-3), R⁷And R⁸It is identical or different, it indicates and phase in formula (IIIa) and formula (IIIb) Those of with.

As the typical example of above-mentioned formula (III-1) compound represented, can enumerate：Monoallyl diglycidyl isocyanide Bis- (2- methylglycidyls) isocyanuric acid esters of urea acid esters, 1- allyls -3,5-, 1- (2- methylpropenyls) -3,5- two shrink Glyceryl isocyanuric acid ester, bis- (2- methylglycidyls) isocyanuric acid esters of 1- (2- methylpropenyls) -3,5- etc..

As the typical example of above-mentioned formula (III-2) compound represented, can enumerate：Diallyl list glycidyl isocyanide Bis- (2- the methylpropenyls) -5- of urea acid esters, 1,3- diallyls -5- (2- methylglycidyls) isocyanuric acid ester, 1,3- shrink Bis- (2- methylpropenyls) -5- (2- methylglycidyls) isocyanuric acid esters of glyceryl isocyanuric acid ester, 1,3- etc..

As the typical example of above-mentioned formula (III-3) compound represented, can enumerate：Triglycidyl group isocyanuric acid ester, Three (2- methylglycidyls) isocyanuric acid esters etc..

It should be noted that alcohol, acid anhydrides etc. and epoxy reaction can also be added in above-mentioned isocyanuric acid derivative (H) Compound and use after being modified in advance.

Wherein, as isocyanuric acid derivative (H), go out from the light reflective of solidfied material, heat resistance and deliquescent viewpoint Hair, preferably above-mentioned formula (III-1)~(III-3) compound represented are more preferably chemical combination shown in above-mentioned formula (III-1) Object.It should be noted that in the hardening resin composition of the present invention, isocyanuric acid derivative (H) can be used alone, It can also be used in combination of two or more.Wherein, it as isocyanuric acid derivative (H), can also use for example：Trade name " TEPIC " (Nissan Chemical Industries (strain) system)；Trade name " MA-DGIC ", " DA-MGIC " are (above by four countries' chemical conversion industry (strain) System) etc. commercially available products.

Relative to hardening resin composition (100 weight %), the isocyanide urea in hardening resin composition of the invention The content (use level) of acid derivative (H) is preferably 0.05~15 weight %, is more preferably 0.1~10 weight %, is further excellent It is selected as 0.3~5 weight %.By making the content of isocyanuric acid derivative (H) in above range, heat resistance and fast light can be obtained The excellent solidfied material of property.

The content (use level) of isocyanuric acid derivative (H) in the hardening resin composition of the present invention is without special limit It is fixed, but relative to 100 parts by weight of total amount for the compound with epoxy group for including in hardening resin composition, preferably 1 ~60 parts by weight, more preferably 1~50 parts by weight, further preferably 1~30 parts by weight.By making isocyanuric acid derivative (H) content can obtain the solidfied material of heat resistance and excellent in light-resistance in above range.

[intramolecular has the silicone derivative (I) of 2 or more epoxy groups]

The silicone derivative (I) of the neccessary composition of hardening resin composition as the present invention, which is intramolecular, has 2 A above epoxy group and the compound (silicone compounds) with the skeleton formed by siloxanes key (- Si-O-Si-).As Siloxane backbone (Si-O-Si skeletons) in silicone derivative (I), is not particularly limited, it can be mentioned, for example：Annular siloxane Skeleton；Silicone matrix such as the polysilsesquioxane of the siloxanes of straight-chain, cage modle or ladder type etc..Wherein, as above-mentioned silicon Oxygen alkane skeleton inhibits the luminosity of optical semiconductor device to decline from making the light reflective of solidfied material, heat resistance, light resistance improve Viewpoint is set out, preferably annular siloxane skeleton, straight-chain siloxane backbone.That is, as silicone derivative (I), preferably Annular siloxane, intramolecular straight-chain siloxanes with 2 or more epoxy group of the intramolecular with 2 or more epoxy groups.

In the case that silicone derivative (I) is the annular siloxane that intramolecular has 2 or more epoxy groups, the silicon is formed The number of the Si-O units of oxygen alkane ring is not particularly limited (equal to the number for the silicon atom for forming silicone ring), but from making solidfied material Heat resistance, light resistance improve from the perspective of, preferably 2~12, more preferably 4~8.

The weight average molecular weight of silicone derivative (I) is not particularly limited, but from making the heat resistance of solidfied material, light resistance carry From the perspective of height, preferably 100~3000, more preferably 180~2000.It should be noted that silicone derivative (I) Above-mentioned weight average molecular weight can be calculated by the molecular weight of the standard polystyren conversion measured using GPC (gel permeation chromatography) method.

The number for the epoxy group that the intramolecular of silicone derivative (I) has is 2 or more, is not particularly limited, But from the viewpoint of so that the heat resistance of solidfied material, light resistance is improved, preferably 2~4 (2,3 or 4).

The epoxide equivalent of silicone derivative (I) is not particularly limited, but from making the heat resistance of solidfied material, light resistance improve From the perspective of, preferably 180~2000, more preferably 180~1500, further preferably 180~1000.It needs to illustrate It is that above-mentioned epoxide equivalent is the value measured based on JIS K7236.

For epoxy group possessed by silicone derivative (I), though it is not particularly limited, from making the heat-resisting of solidfied material Property, from the perspective of light resistance improves, the epoxy group that is preferably made of adjacent 2 carbon atoms and oxygen atom that constitute alicyclic ring (ester ring oxygroup), wherein particularly preferably epoxycyclohexyl.

As silicone derivative (I), it can be mentioned, for example silicone compounds etc. shown in following formula (IV)s.

[chemical formula 16]

In formula (IV), R^aIt is identical or different, indicate group or alkyl containing epoxy group.Also, the R in formula (IV)^a's At least two (such as 2~4) is the group containing epoxy group.The above-mentioned group containing epoxy group is to include at least 1 epoxy group The group of (oxirane ring), it can be mentioned, for example：Alkenyl etc. has the aliphatic of the straight or branched of carbon-to-carbon unsaturated double-bond At least one double bond possessed by alkyl through group made of epoxidation, with the cricoid aliphatic hydrocarbon of carbon-to-carbon unsaturated double-bond Base is (for example, cycloalkenyl group；Cycloalkenyl alkyls such as cyclohexenylethyl etc.) possessed by least one double bond through base made of epoxidation Group etc..More specifically, it can be mentioned, for example：1,2- epoxy ethyls (epoxy group), 1,2- the glycidyl, (contracting of 2,3- glycidyl Water glyceryl), 2,3- epoxy -2- methyl-propyls (methylglycidyl), 3,4- epoxybutyls, 3- glycidoxypropyls third Base, 3,4- epoxycyclohexyl-methyls, 2- (3,4- epoxycyclohexyls) ethyl etc..Wherein, it is however preferred to have carbon-to-carbon unsaturated double-bond Cricoid aliphatic alkyl possessed by least one double bond through group made of epoxidation.As abovementioned alkyl, can enumerate： The carbon atom numbers such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, iso-octyl, decyl, dodecyl 1~20 it is straight The alkyl etc. of chain or branched.Wherein, the preferably alkyl of the straight or branched of carbon atom number 1~10.

In formula (IV), n indicates 2~12 integer.In particular, from the thermal shock resistance of solidfied material, optical semiconductor device From the viewpoint of resistance to reflow and thermal shock resistance, as n, preferably 4~8, more preferably 4 or 5.

As silicone derivative (I), more specifically, it can be mentioned, for example：[2- (3- { the oxabicyclos of 2,4- bis- [4.1.0] heptyl }) ethyl] -2,4,6,6,8,8- hexamethyls-cyclotetrasiloxane, the [2- (3- { oxabicyclos [4.1.0] of 4,8- bis- Heptyl }) ethyl] -2,2,4,6,6,8- hexamethyls-cyclotetrasiloxane, [the 2- (3- { oxabicyclo [4.1.0] heptyl }) of 2,4- bis- Ethyl] -6,8- dipropyl -2,4,6,8- tetramethyls-cyclotetrasiloxane, [the 2- (3- { oxabicyclo [4.1.0] heptyl }) of 4,8- bis- Ethyl] -2,6- dipropyl -2,4,6,8- tetramethyls-cyclotetrasiloxane, 2,4,8- tri- [2- (3- { oxabicyclo [4.1.0] heptan Base }) ethyl] -2,4,6,6,8- pentamethyls-cyclotetrasiloxane, [2- (3- { oxabicyclo [4.1.0] the heptyl }) second of 2,4,8- tri- Base] -6- propyl -2,4,6,8- tetramethyls-cyclotetrasiloxane, [2- (3- { oxabicyclo [4.1.0] the heptyl }) second of 2,4,6,8- tetra- Base] silsesquioxane etc. of -2,4,6,8- tetramethyls-cyclotetrasiloxane, intramolecular with 2 or more epoxy groups.It is more specific and Speech, it can be mentioned, for example the annular siloxanes etc. that intramolecular shown in following formula has 2 or more epoxy groups.

[chemical formula 17]

In addition, as silicone derivative (I), can also use for example：Remember in Japanese Unexamined Patent Publication 2008-248169 bulletins Have extremely in 1 molecule described in the organic siliconresin of the oxygroup containing ester ring that carries, Japanese Unexamined Patent Publication 2008-19422 bulletins Organic polysilsesquioxane resins etc. of few 2 epoxy functional groups.

It should be noted that in the hardening resin composition of the present invention, silicone derivative (I) can be used alone one Kind, it can also be used in combination of two or more.

For silicone derivative (I), what can be obtained has for example：There is 2 or more epoxy groups as intramolecular The trade name " X-40-2678 " of annular siloxane, " X-40-2670 ", " X-40-2720 " are (above by SHIN-ETSU HANTOTAI's chemical industry (strain) System) etc. commercially available products.In addition, silicone derivative (I) can be manufactured by known or customary way.

Relative to hardening resin composition (100 weight %), the siloxanes in hardening resin composition of the invention The content (use level) of derivative (I) is preferably 0.1~30 weight %, more preferably 0.5~20 weight %, is more preferably 1.0~10 weight %.By the way that the content of silicone derivative (I) is controlled in above range, there are hardening resin compositions Thixotropy improve, the tendency that heat resistance, light resistance and the light reflective of solidfied material further increase.

The content (use level) of silicone derivative (I) in the hardening resin composition of the present invention is without special limit It is fixed, but relative to 100 parts by weight of total amount for the compound with epoxy group for including in hardening resin composition, preferably 5 ~99 parts by weight, more preferably 10~95 parts by weight, further preferably 20~80 parts by weight.By making silicone derivative (I) content is 5 parts by weight or more, and there are the raising of the thixotropy of hardening resin composition, heat resistance, the lights resistance of solidfied material And the tendency that light reflective further increases.On the other hand, by make silicone derivative (I) content be 150 parts by weight with Under, there are the tendencies that the thermal shock resistance of solidfied material and cementability further increase.

[releasing agent]

Releasing agent can also be further included in the hardening resin composition of the present invention.By comprising releasing agent, being easy Realization has used the continuously shaped of the method for forming of mold based on transfer molding etc., and solidfied material (reflection can be manufactured with high productivity Body).As releasing agent, known or usual releasing agent can be used, be not particularly limited, it can be mentioned, for example：Fluorine class release agent (contains The compound of fluorine atom；For example, fluorocarbon oil, polytetrafluoroethylene (PTFE) etc.), the releasing agent (organo-silicon compound of organic silicon；For example, silicon Oil, silicon wax, organic siliconresin, the organopolysiloxane etc. with polyalkylene oxide units), wax class releasing agent (wax class；For example, bar The paraffin class such as the animal waxs such as the vegetable waxs such as western palm wax, lanocerin, paraffin, polyethylene wax, oxidized polyethylene wax etc.), advanced fat Fat acid or its salt (for example, metal salt etc.), high-grade aliphatic ester, higher fatty acid amides, mineral oil etc..

It should be noted that in the hardening resin composition of the present invention, releasing agent can be used alone, can also It is used in combination of two or more.In addition, releasing agent can both utilize known or customary way to manufacture, can also use commercially available Product.

In the case that the hardening resin composition of the present invention contains releasing agent, the content (use level) of releasing agent is without spy It is different to limit, but relative to 100 parts by weight of total amount for the compound with epoxy group for including in hardening resin composition, preferably For 1~12 parts by weight, more preferably 2~10 parts by weight.Content by making releasing agent is 1 parts by weight or more, and there are solidfied materials The tendency that the release property of (reflector) further increases, the productivity of reflector further increases.On the other hand, by making demoulding The content of agent is 12 parts by weight hereinafter, in the presence of the reflector that can be ensured on optical semiconductor board for mounting electronic relative to lead The tendency of the good adaptation of frame.

[antioxidant]

The hardening resin composition of the present invention can also include antioxidant.By that comprising antioxidant, can manufacture The solidfied material (reflector) of excellent heat resistance.As antioxidant, known or usual antioxidant can be used, it is not special It limits, it can be mentioned, for example：Phenol antioxidant (phenolic compound), hindered amines antioxidant (hindered amine compound), phosphorus Class antioxidant (phosphorus species), sulphur class antioxidant (sulphur class compound) etc..

As phenol antioxidant, it can be mentioned, for example：2,6- toluene di-tert-butyl phenols, butylated hydroxyanisol, 2, The single phenols classes such as 6- di-t-butyls paraethyl phenol, stearyl-β-(3,5- di-tert-butyl-hydroxy phenyls) propionic ester；2,2 '-is sub- Methyl bis- (4- methyl-6-tert-butylphenols), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol)s, 4,4 '-thiobis (3- Methyl-6-tert-butylphenol), 4,4 '-fourths pitch bis- (3 methy 6 tert butyl phenols), the bis- [1,1- dimethyl -2- { β-of 3,9- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy } ethyl] bis-phenols such as 2,4,8,10- tetra- oxaspiro [5.5] hendecane Class；1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane, (the bis- tertiary fourths of 3,5- of 1,3,5- trimethyls -2,4,6- three Base -4- hydroxybenzyls) benzene, four-[methylene -3- (3 ', 5 '-di-t-butyls -4 '-hydroxy phenyl) propionic ester] methane, it is bis- [3, 3 '-bis- (4 '-hydroxyls -3 '-tert-butyl-phenyl) butyric acid] glycol ester, (3 ', the 5 '-di-t-butyls -4 '-hydroxyl benzyl of 1,3,5- tri- Base)-guanamine, polymer electrolytes phenols such as 4,6- (1H, 3H, 5H) triketone, tocopherol etc..

As hindered amines antioxidant, it can be mentioned, for example：Bis- (1,2,2,6,6- pentamethyl -4- piperidyls) [[3,5- is bis- (1,1- dimethyl ethyls) -4- hydroxy phenyls] methyl] butylmalonic acid ester, bis- (1,2,2,6,6- pentamethyl -4- piperidyls) last of the ten Heavenly stems Two acid esters, methyl-1,2,2,6,6- pentamethyl -4- piperidinyl sebacates, 4 benzoyloxy 2,2,6,6 tetramethyl piperidine Deng.

As phosphorus antioxidants, it can be mentioned, for example：Triphenyl phosphite, diphenylisodecyl base ester, phosphorous acid Phenyl diiso decyl ester, phosphorous acid three (nonyl phenyl) ester, diiso decyl the pentaerythritol phosphite, (2,4- bis- of phosphorous acid three Tert-butyl-phenyl) ester, bis- (octadecyl) phosphite esters of cyclic annular four base of neopentane, bis- (the bis- tertiary fourths of 2,4- of ring-type four base of neopentane Base phenyl) phosphite ester, bis- (2,4- di-t-butyl -4- aminomethyl phenyls) phosphite esters of cyclic annular four base of neopentane, bis- [tertiary fourths of 2- Base -6- methyl -4- { 2- (octadecane epoxide carbonyl) ethyl } phenyl] phosphorous acid esters such as H-Phosphonate；9,10- dihydros -9- Oxa- -10- phospho hetero phenanthrene -10- oxides, the miscellaneous -10- phosphorus of 10- (3,5- di-tert-butyl-4-hydroxyl benzyls) -9,10- dihydro-9-oxies The oxa-s phospho hetero phenanthrenes such as miscellaneous phenanthrene -10- oxides are oxide-based etc..

As sulphur class antioxidant, it can be mentioned, for example：Lauryl mercaptan, dilauryl -3,3 '-thiodipropionate, Myristyl -3,3 '-thiodipropionate, distearyl -3,3 '-thiodipropionate etc..

In the hardening resin composition of the present invention, antioxidant can be used alone, can also will be two or more It is applied in combination.In addition, antioxidant can both be manufactured by known or customary way, such as trade name can also be used " Irganox1010 " (BASF systems, phenol antioxidant), trade name " AO-60 ", " AO-80 " ((strain) ADEKA systems, phenols antioxygen Agent), trade name " Irgafos168 " (BASF systems, phosphorus antioxidants), trade name " ADK STAB HP-10 ", " ADK STAB PEP-36 " ((strain) ADEKA systems, phosphorus antioxidants), trade name " HCA " (three light (strain) system, phosphorus antioxidants) etc. Commercially available product.

In the case that the hardening resin composition of the present invention contains antioxidant, the content (use level) of antioxidant does not have There is a particular determination, but relative to 100 parts by weight of total amount for the compound with epoxy group for including in hardening resin composition, Preferably 0.1~5 parts by weight, more preferably 0.5~3 parts by weight.By making the content of antioxidant be 0.1 parts by weight or more, It can be effectively prevented the oxidation of solidfied material (reflector), there are the tendencies that heat resistance, light resistance further increase.On the other hand, By make antioxidant content be 5 parts by weight hereinafter, in the presence of be easy to get coloring be inhibited, the more good reflection of form and aspect The tendency of body.

[additive]

It, can also be in the effect for not destroying the present invention other than mentioned component in the hardening resin composition of the present invention Contain various additives in the range of fruit.As above-mentioned additive, containing such as ethylene glycol, diethylene glycol, propylene glycol, glycerine Deng with hydroxyl compound (in particular, aliphatic polyol) when, reaction can be made slowly to carry out.In addition to this, also may be used To use antifoaming agent, levelling agent, γ-glycidoxypropyl group trimethoxy silicon in the range of not destroying viscosity, light reflective The silane coupling agents such as alkane or 3-mercaptopropyi trimethoxy silane, surfactant, fire retardant, colorant, ionic adsorption body, purple The usual additives such as the pigment other than ultraviolet absorbers, light stabilizer, white pigment (C).The content of these additives does not have Particular determination can be selected suitably.

The hardening resin composition of the present invention contains cycloaliphatic epoxy (A), rubber particles (B), white pigment (C), inorganic filler (D), curing agent (E), curing accelerator (F), isocyanuric acid derivative (H) and silicone derivative (I) In the case of, for including cycloaliphatic epoxy (A), rubber particles (B), curing agent (E), curing accelerator (F), isocyanide The mixture of urea acid derivative (H) and silicone derivative (I) is not particularly limited in 25 DEG C of viscosity, but preferably 5000mPas or less.It should be noted that the hardening resin composition of the present invention can also include that ethylene glycol etc. is above-mentioned Aliphatic polyol, in this case, above-mentioned mixture are comprising cycloaliphatic epoxy (A), rubber particles (B), consolidate The mixing of agent (E), curing accelerator (F), isocyanuric acid derivative (H), silicone derivative (I) and aliphatic polyol Object.

On the other hand, hardening resin composition of the invention contain cycloaliphatic epoxy (A), rubber particles (B), White pigment (C), inorganic filler (D), curing catalysts (G), isocyanuric acid derivative (H) and silicone derivative (I) In the case of, for including cycloaliphatic epoxy (A), rubber particles (B), curing catalysts (G), isocyanuric acid derivative (H) and the mixture of silicone derivative (I) is not particularly limited in 25 DEG C of viscosity, but preferably 5000mPas or less. It should be noted that in the present specification, two kinds of above-mentioned mixtures are referred to as " resin viscosity " in 25 DEG C of viscosity sometimes.

Above-mentioned resin viscosity is under normal pressure in the viscosity of 25 DEG C of measurement.Above-mentioned resin viscosity be preferably 5000mPas with Under, more preferably 4000mPas or less, further preferably 3500mPas or less, particularly preferably 3000mPas with Under.When above-mentioned resin viscosity is 5000mPas or less, compared with the case where resin viscosity is more than 5000mPas, there is solidification Heat resistance, light resistance and resistance to cracking (especially excellent heat resistance) more excellent tendency of object.In addition, above-mentioned by making Resin viscosity it is relatively low, it can be achieved that the content of other ingredients such as white pigment (C), inorganic filler (D) increase, thus exist solid The tendency that light reflective, heat resistance and the light resistance of compound further improve.The lower limit of above-mentioned resin viscosity is, for example, 100mPas or more.It should be noted that above-mentioned resin viscosity for example can be used Digital Viscometer (model " DVU-EII types ", (strain) Tokimec systems), in rotor:Standard 1 ° of 34 ' × R24, temperature:25 DEG C, rotating speed:It is surveyed under conditions of 0.5~10rpm It is fixed.

Above-mentioned resin viscosity for example can by using at 25 DEG C be liquid ingredient as used ingredient (for example, fat Ring type epoxide (A), curing agent (E), curing accelerator (F), curing catalysts (G), isocyanuric acid derivative (H) and Silicone derivative (I) etc.) and be readily available.It should be noted that as mentioned component, it is solid that can also use at 25 DEG C The ingredient of body, but its content is preferably adjusted to so that above-mentioned resin viscosity reaches 5000mPas or less.Furthermore it is also possible to logical It crosses and the content of rubber particles (B) is adjusted in the range of not destroying the effect of the present invention and is readily available.

It should be noted that the hardening resin composition of the present invention can also be to make the curability by being heated A part for cycloaliphatic epoxy (A) and curing agent (E) in resin combination react obtained from, have passed through B The hardening resin composition (hardening resin composition of B scalariform states) of rank.

As described above, the hardening resin composition of the present invention is due to light reflective, heat resistance and the light resistance after solidification It is excellent, therefore can particularly preferably be used as transfer molding resin combination or compression forming resin combination.Wherein, due to The light reflective of the solidfied material (reflector) that is formed by compression forming of hardening resin composition of the present invention, heat resistance and Light resistance is especially excellent, therefore the resin combination of particularly preferably compression forming.

Though be not particularly limited, the present invention hardening resin composition can by by above-mentioned each ingredient according to need It wants and is stirred in the state of being heated, mixes and prepare.It should be noted that the just curable resin combination of the present invention For object, can by directly use be pre-mixed by each ingredient made of mixture single-component system composition in the form of make With two or more ingredient respectively pre-saved can also being used in mixed way to certainty ratio before the use with for example multigroup The form of the composition of fission system (for example, bicomponent system) uses.Above-mentioned stirring, mixing method be not particularly limited, can Using known in such as various mixing machines such as dissolvers, homogenizer, kneader, roller, ball mill, rotation-revolution formula agitating device etc. or Usual stirring/mixing mechanism.Alternatively, it is also possible to after stirring, mixing, carry out deaeration under vacuum.

Though being not particularly limited, group of the rubber particles (B) preferably to be scattered in advance in cycloaliphatic epoxy (A) The state for closing object (being also known as the composition " being dispersed with the epoxide of rubber particles ") is coordinated.That is, the present invention Hardening resin composition is preferably by by the above-mentioned epoxide for being dispersed with rubber particles, white pigment (C), inorganic fill Agent (D), curing agent (E) and curing accelerator (F) or curing catalysts (G) and other ingredients as needed, which are mixed, to be come It prepares.Preparation method in this way, especially it is possible to make the dispersibility of the rubber particles (B) in hardening resin composition It improves.But it should be recognized that the fitting method of rubber particles (B) is not limited to the above method, can also be independent with it The method that is coordinated of form.

(epoxide for being dispersed with rubber particles)

The above-mentioned epoxide for being dispersed with rubber particles can be closed by making rubber particles (B) be scattered in alicyclic epoxy It is obtained in object (A).It should be noted that the above-mentioned cycloaliphatic epoxy being dispersed in the epoxide of rubber particles (A) can also be partial amount either constituting the whole amount of the cycloaliphatic epoxy (A) of hardening resin composition. Similarly, the above-mentioned rubber particles (B) being dispersed in the epoxide of rubber particles are either constitute curable resin group The whole amount for closing the rubber particles (B) of object, can also be partial amount.

The viscosity of the above-mentioned epoxide for being dispersed with rubber particles for example can be by being applied in combination reactive diluent It is adjusted (that is, reactive diluent can also be further included by being dispersed with the epoxide of rubber particles).As above-mentioned Reactive diluent is preferably that 200mPas aliphatic poly shrinks below are sweet using the viscosity under such as room temperature (25 DEG C) Oily ether.As viscosity, (25 DEG C) are 200mPas aliphatic polyglycidyl ethers below, it can be mentioned, for example：Hexamethylene diformazan Alcohol diglycidyl ether, cylohexanediol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-HD 2-glycidyl Ether, trihydroxymethylpropanyltri diglycidyl ether, polypropylene glycol diglycidyl ether etc..

The usage amount of above-mentioned reactive diluent can be adjusted suitably, be not particularly limited, but relative to above-mentioned point Dissipating has 100 parts by weight of epoxide total amount of rubber particles, below preferably 30 parts by weight, below more preferably 25 parts by weight (for example, 5~25 parts by weight).When usage amount is 30 parts by weight or less, exists and be easy to get obdurability (resistance to cracking) raising etc. The tendency of desired performance.

The manufacturing method of the above-mentioned epoxide for being dispersed with rubber particles is not particularly limited, and can be used known usual Method.It can be mentioned, for example：It is mixed into alicyclic epoxy after powder is made and closes being dehydrated rubber particles (B) In object (A) and and the method that makes it disperse, the lotion of rubber particles (B) is directly mixed with cycloaliphatic epoxy (A), is right The method etc. being dehydrated afterwards.

The hardening resin composition of the present invention is not particularly limited in 25 DEG C of viscosity, but preferably 100~ 1000000mPas, more preferably 200~800000mPas, further preferably 300~800000mPas.By making Viscosity at 25 DEG C is 100mPas or more, and there are operability when casting to improve, the heat resistance of solidfied material and light resistance are into one Walk the tendency improved.On the other hand, by making the viscosity at 25 DEG C for 1000000mPas hereinafter, there is operation when casting Property improve, solidfied material be more not susceptible to by cast it is bad caused by unfavorable condition tendency.

The hardening resin composition solidification for making the present invention by heated by, it is excellent to obtain light reflective, heat-resisting Property, light resistance and the excellent solidfied material of resistance to cracking.It should be noted that the hardening resin composition of the present invention will be made sometimes The solidfied material of solidfied material made of solidification, the i.e. hardening resin composition of the present invention is known as " solidfied material of the invention ".Solidification When heating temperature (solidification temperature) be not particularly limited, but preferably 50~200 DEG C, more preferably 80~180 DEG C.In addition, The time (hardening time) heated when solidification is not particularly limited, but preferably 60~1800 seconds, more preferably 90~900 seconds. In the case of the lower limiting value of solidification temperature and hardening time less than above range, may cause to cure it is insufficient, on the contrary, in height In the case of the upper limit value of above range, may xanthochromia be caused by thermal decomposition, it is not preferable.Condition of cure is dependent on various Condition, but for example in the case where improving solidification temperature can by shorten hardening time, in the feelings for reducing solidification temperature It can suitably be adjusted bys increasing hardening time etc. under condition.In addition, curing process can both pass through a stage (example Such as, compression forming is only carried out) and carry out, it can also be for example, by multiple stages (for example, curing after being used as after compression forming (secondary curing) and further heated etc. using baking oven etc.) carry out.In addition, in the case of cured after carrying out, at this time Heating temperature is preferably 50~200 DEG C, more preferably 60~180 DEG C, the temperature more preferably with solidification temperature equal extent.Separately Outside, the cured time is preferably 0.5~10 hour, more preferably 1~8 hour after progress.

The solidfied material of the present invention has high light reflective, heat resistance and excellent in light-resistance.Above-mentioned solidfied material is not easy as a result, Deteriorate, be not susceptible to reflectivity through when reduce.Therefore, hardening resin composition of the invention is preferably used as LED Encapsulate purposes (constituent material of LED encapsulation piece, such as reflector material, case material etc. in optical semiconductor device), electronics The bonding purposes of component, liquid crystal display purposes (for example, reflecting plate etc.), white substrate ink, sealant etc..Wherein, may be used Particularly preferably the hardening resin composition as LED encapsulation is (in particular, the solidification of the reflector in optical semiconductor device Property resin combination (that is, hardening resin composition of reflector formation)).

The reflectivity (initial stage reflectivity) of the solidfied material of the present invention is not particularly limited, for example, the light of wavelength 450nm is anti- The rate of penetrating is preferably 93% or more, more preferably 94% or more, further preferably 95% or more.In particular, 450~800nm The reflectivity of light is preferably 93% or more, more preferably 94% or more, further preferably 95% or more.

The solidfied material of the present invention (also referred to as " adds the reflectivity of the light of wavelength 450nm after being heated 250 hours at 120 DEG C Reflectivity after heat ageing ") conservation rate ([reflectivity after heat ageing]/[initial stage reflectivity] relative to initial stage reflectivity × 100) it is not particularly limited, but preferably 80% or more, more preferably 85% or more, further preferably 90% or more.It is special It is not that the conservation rate in the case of the light of 450~800nm is preferably 80% or more, is more preferably 85% or more, further preferably It is 90% or more.Hardening resin composition according to the present invention can make the upper of the solidfied material formed by compression forming It states conservation rate and reaches 90% or more.

The solidfied material of the present invention is through intensity 10mW/cm²Ultraviolet light irradiate 250 hours after to the light of wavelength 450nm Conservation rate ([ultraviolet ray ageing after of the reflectivity (also referred to as " reflectivity after ultraviolet ray ageing ") relative to initial stage reflectivity Reflectivity]/[initial stage reflectivity] × 100) be not particularly limited, but preferably 80% or more, more preferably 85% or more, into one Step preferably 90% or more.In particular, the conservation rate in the case of the light of 450~800nm is preferably 80% or more, is more preferably 85% or more, it is more preferably 90% or more.

It should be noted that above-mentioned reflectivity for example can be by the solidfied material (thickness of the present invention:3mm) be used as test film, It is measured using spectrophotometer (trade name " spectrophotometer UV-2450 ", (strain) Shimadzu Seisakusho Ltd. system).

The hardening resin composition of the present invention is the hardening resin composition of the reflector in optical semiconductor device In the case of, hardening resin composition of the invention is the substrate for the optical semiconductor being used to form in optical semiconductor device The moulding material of the purposes of reflector (light reflecting member) possessed by (optical semiconductor board for mounting electronic) is (for utilizing mould Tool etc. carries out molding material).Therefore, by the way that the hardening resin composition of the present invention is molded (and making its solidification), It can produce and have the Gao Pin with high light reflectivity, heat resistance and excellent in light-resistance and the excellent reflector of resistance to cracking Matter (such as high-durability) optical semiconductor board for mounting electronic.It should be noted that the reflector is in light Make in semiconductor device the light sent out by optical semiconductor occur reflection and improve light directive property and brightness, to make light Export the component that efficiency improves.Sometimes the reflector at least with the solidfied material formation for utilizing the present invention is used for photosemiconductor The substrate of element mounting purposes is known as " optical semiconductor board for mounting electronic of the invention ".

The optical semiconductor board for mounting electronic of the present invention is the hardening resin composition at least having using the present invention The reflector that is formed of solidfied material (solidfied material as obtained from the hardening resin composition solidification for making the present invention) (white is anti- Beam) substrate.Fig. 1 is the schematic diagram of an example for showing the optical semiconductor board for mounting electronic of the present invention, and (a) indicates three-dimensional Figure, (b) indicate sectional view.100 in Fig. 1 indicate that white reflector, 101 indicate that metal wiring (lead frame), 102 indicate light half The carrying region of conductor element, 103 indicate package substrate.It should be noted that being equipped with metal wiring on package substrate 103 101 and it is further fitted with white reflector 100, (the carrying region 102 of optical semiconductor) is provided with light half at its center Conductor element 107 simultaneously have passed through chip welding, lead between the metal wiring 101 on optical semiconductor 107 and package substrate 103 It crosses wire bonding and connects.As the material of package substrate 103, resin, ceramics etc. can be used, can also be and white reflector Identical material.The white reflector 100 of the upside of the optical semiconductor board for mounting electronic of the present invention is annularly to surround Around the carrying region 102 of optical semiconductor and the diameter of its ring has inclined concavity towards the widened mode in top Shape.For the optical semiconductor board for mounting electronic of the present invention, the inner surface of above-mentioned concave shape is at least by the present invention Hardening resin composition solidfied material formation.In addition, as shown in Figure 1, the part to be fenced up by metal wiring 101 The case where the case where (102 lower parts) had both included package substrate 103 also includes white reflector 100 is (that is, " 100/ in Fig. 1 103 " indicate either white reflector 100, can also be package substrate 103).But it should be recognized that the light of the present invention Substrate for carrying semiconductor components is not limited to embodiment shown in FIG. 1.

As the method for the white reflector in the optical semiconductor board for mounting electronic for forming the present invention, can be used known Or usual forming method (for example, compression forming etc.), it is not particularly limited, it can be mentioned, for example the curable resins for making the present invention Composition undergoes transfer molding, compression forming, injection moulding, LIM moldings (injection moulding), the box dam molding etc. using distributor The method etc. of various forming methods.Cured condition when as formation reflector, such as can be from above-mentioned formation solidfied material When condition etc. in suitably select.In the present invention, wherein from that can prevent from foaming caused by curing reaction drastically, mitigate From the perspective of the stress deformation caused by curing is to make toughness (resistance to cracking) improve, multiple stages is preferably divided to implement heating Processing periodically makes its solidification.

By by the present invention optical semiconductor board for mounting electronic be used as optical semiconductor device in substrate and relative to The substrate and carry optical semiconductor, can be obtained the present invention optical semiconductor device.

The optical semiconductor device of the present invention is that at least have the optical semiconductor as light source and the solidification by the present invention Property resin combination solidfied material formed reflector (reflecting material) optical semiconductor device.More specifically, light of the invention Semiconductor device is the photosemiconductor member at least having the optical semiconductor board for mounting electronic of the present invention and being equipped on the substrate The optical semiconductor device of part.The optical semiconductor device of the present invention is due to the solidification with the hardening resin composition by the present invention Object formed reflector as reflector, therefore be not susceptible to light brightness through when reduce, reliability height.Fig. 2 is to show The schematic diagram (sectional view) of an example of the optical semiconductor device of the present invention.100 in Fig. 2 indicate that white reflector, 101 indicate metal Wiring (lead frame), 103 indicate that package substrate, 104 indicate that closing line, 105 indicate that sealing material, 106 indicate that chip welds material Material, 107 indicate optical semiconductor (LED element).In optical semiconductor device shown in Fig. 2, sent out by optical semiconductor 107 The light gone out can reflect on the surface (reflecting surface) of white reflector 100, therefore can efficiently export by optical semiconductor 107 light sent out.It should be noted that as shown in Fig. 2, the optical semiconductor in the optical semiconductor device of the present invention is usually sharp It is sealed with transparent sealing material (105 in Fig. 2).

Fig. 3,4 are another figures for showing the optical semiconductor device of the present invention.108 in Fig. 3,4 indicate radiating piece (shell radiating piece), by having such radiating piece 108, the exothermal efficiency of optical semiconductor device to improve.Fig. 3 is dissipating for radiating piece Hot path is located at the example of the underface of optical semiconductor, and Fig. 4 is that the heat dissipation path of radiating piece is located at optical semiconductor device Example [(a) indicates that vertical view, (b) indicate the A-A ' sectional views in (a)] in transverse direction.In Fig. 4 in optical semiconductor device Side radiating piece 108 outstanding is also sometimes referred to as cooling fin.In addition, 109 in Fig. 4 indicate cathode mark.It needs to illustrate It is that optical semiconductor device of the invention is not limited to embodiment shown in Fig. 2~4.

Embodiment

Hereinafter, the present invention is described in more detail in conjunction with the embodiments, but the present invention is not limited to these implementations Example.It should be noted that the unit of the use level of each ingredient of hardening resin composition in 1~table of table 3 is parts by weight.Separately Outside, the "-" in 1~table of table 3 indicates not carrying out the cooperation of the ingredient.

Production Example 1

(manufactures of rubber particles)

Feed intake ion exchange water 500g and dioctyl sodium sulphosuccinate into the 1L aggregation containers with reflux condenser 0.68g while being stirred under nitrogen flowing, is warming up to 80 DEG C.It is disposably added thereto for forming rubber particles Core part for necessary amount about 5 weight % amount by butyl acrylate 9.5g, styrene 2.57g and divinylbenzene 0.39g constitute monomer mixture, stirring 20 minutes and make its emulsify after, add potassium persulfate 9.5mg, stir 1 hour And initial seeding polymerization is carried out.Then, potassium persulfate 180.5mg is added, stir within 5 minutes.Spend 2 hours to Wherein continuously addition make dioctyl sodium sulphosuccinate 0.95g be dissolved in for shape nucleation portion necessary amount remaining It is single made of in butyl acrylate 180.5g, the styrene 48.89g and divinylbenzene 7.33g of amount (amounts of about 95 weight %) Body mixture carries out secondary seeding polymerization, then carries out curing in 1 hour and has obtained core part.

Then, it adds potassium persulfate 60mg and stirs 5 minutes, spending 30 minutes, continuously addition makes dioctyl thereto Sodium sulfosuccinate 0.3g be dissolved in methyl methacrylate 60g, acrylic acid 1.5g and allyl methacrylate 0.3g and At monomer mixture, carried out seeding polymerization.Thereafter, it carries out curing for 1 hour, forms the shell of cladding core part.

Then, (25 DEG C) are cooled to room temperature, is filtered and is wrapped for 120 μm of plastics net by using mesh Latex containing the rubber particles with nucleocapsid.Gained latex is freezed in subzero 30 DEG C, using suction strainer into After row dehydration washing, in one day night of 60 DEG C of forced air dryings, rubber particles have been obtained.The average grain diameter of gained rubber particles is 108nm, maximum particle diameter 289nm.

It should be noted that the average grain diameter of rubber particles, maximum particle diameter are determining as follows：Use is dissipated with dynamic optical Penetrate " the Nanotrac that method is measuring principle^TM" form Nanotrac particle size distribution devices (trade name " UPA-EX150 ", Day machine dress (strain) system) sample is measured, in gained size distribution curve, grain size at the time of accumulation curve is reached 50%, i.e. Cumulative mean grain size is as average grain diameter, maximum grain at the time of by the frequency (%) of particle size distribution result more than 0.00% Diameter is as maximum particle diameter.It should be noted that as said sample, having used makes what is obtained in following Production Examples 2 to be dispersed with 1 parts by weight of epoxide of rubber particles are scattered in sample made of 20 parts by weight of tetrahydrofuran.

Production Example 2

(manufacture for being dispersed with the epoxide of rubber particles)

By 5 parts by weight of rubber particles obtained in Production Example 1 using molten in nitrogen stream, in the state of being heated up to 60 DEG C Solution device and be scattered in trade name " CELLOXIDE 2021P " (3,4- epoxycyclohexyl-methyls (3,4- epoxies) naphthenic acid ester, (strain) Daicel systems) in 100 parts by weight (1000rpm, 60 minutes), vacuum defoamation is carried out, has obtained being dispersed with rubber particles Epoxide (the viscosity at 25 DEG C:1036mPa·s).

It should be noted that the epoxide for being dispersed with rubber particles obtained in Production Example 2 (makes the rubber of 5 parts by weight Micelle, which is scattered in the CELLOXIDE 2021P of 100 parts by weight, to be formed) 25 DEG C at viscosity be use Digital Viscometer (trade name " DVU-EII types ", (strain) Tokimec systems) and measure.

Production Example 3

According to mixing ratio (unit shown in table 1 and table 2:Parts by weight) by trade name " RIKACID MH-700 " (new day This physics and chemistry (strain) is made), trade name " U-CAT 18X " (San-Apro (strain) systems) and ethylene glycol (and Wako Pure Chemical Industries (strain) are made) Utilize rotation-revolution formula agitating device (trade name " practicing Taro agitator (あわとり Practice Taros) AR-250 ", (strain) THINKY systems) it mixes to uniform, it carries out deaeration and has obtained curing agent composition.

Embodiment 1

According to mixing ratio (unit shown in table 1:Parts by weight) rubber particles that are dispersed with that will obtain in Production Example 2 Epoxide, isocyanuric acid derivative (monoallyl diglycidyl isocyanuric acid ester；Trade name " MA-DGIC ", four countries Chemical conversion industry (strain) make), silicone derivative (intramolecular have 2 epoxy groups silicone derivative；Trade name " X-40- 2678 " use rotation-revolution formula agitating device (trade name " practicing Taro agitator AR-250 ", (strain) THINKY systems) mixing It is extremely uniform, deaeration is carried out, mixture has been made.Wherein, it in order to make MA-DGIC dissolve, stirs 1 hour and implements in 80 DEG C State mixing.

Then, according to mixing ratio (unit shown in table 1:Parts by weight) by mixture obtained above and white pigment (titanium oxide；Trade name " DCF-T-17050 ", Resino Color Industry (strain) system), inorganic filler (silica； Trade name " FB-970FD ", Denka (strain) systems) it is mixed to uniform using dissolvers, and utilize roller mill (roller under prescribed conditions Spacing:0.2mm, rotating speed:25 hertz, 3 channels) melting mixing is carried out, obtain mixture.

Then, to reach mixing ratio (unit shown in table 1:Parts by weight) mode by mixture obtained above and Using rotation-revolution formula agitating device, (trade name " practices Taro agitator AR- to the curing agent composition obtained in Production Example 3 250 ", (strain) THINKY systems) it mixes to uniform (2000rpm, 5 minutes), carry out deaeration, obtain hardening resin composition.

Using the mold release film formed by polyester above-mentioned hardening resin composition is sandwiched, is placed in 150 DEG C and is compressed into In type molds, heating in 600 seconds and pressurization are carried out with the pressure of 3.0MPa, followed by cure (at 150 DEG C 5 hours) afterwards, Result in solidfied material.

Embodiment 2~14, comparative example 1~15

In addition to by hardening resin composition with other than being combined into and changing as shown in table 1 or table 2, with implementation Example 1 has got similarly solidfied material.It should be noted that in the Examples and Comparative Examples of part, as curable resin group The constituent for closing object, instead of the epoxide for being dispersed with rubber particles obtained in Production Example 2 or together in Production Example 2 In the obtained epoxide for being dispersed with rubber particles together, used alicyclic epoxy shown in table 1 or table 2 to close Object.

Embodiment 15

According to mixing ratio (unit shown in table 1:Parts by weight) rubber particles that are dispersed with that will obtain in Production Example 2 Epoxide, isocyanuric acid derivative (monoallyl diglycidyl isocyanuric acid ester；Trade name " MA-DGIC ", four countries Chemical conversion industry (strain) make), silicone derivative (intramolecular have 2 epoxy groups silicone derivative；Trade name " X-40- 2678 ", SHIN-ETSU HANTOTAI's chemical industry (strain) is made) using rotation-revolution formula agitating device, (trade name " practices Taro agitator AR- 250 ", (strain) THINKY systems) it mixes to uniform, deaeration is carried out, mixture has been made.Wherein, in order to make MA-DGIC dissolve, in 80 DEG C are stirred 1 hour and implement above-mentioned mixing.

Then, to reach mixing ratio (unit shown in table 1:Parts by weight) mode by mixture obtained above and solid Change catalyst (trade name " San Aid SI-100L ", three new chemical industry (strain) systems) and uses rotation-revolution formula agitating device (quotient The name of an article " practice Taro agitator AR-250 ", (strain) THINKY systems) it mixes to uniform (2000rpm, 5 minutes), carry out deaeration, Hardening resin composition is obtained.

Embodiment 16, comparative example 16~24

In addition to by hardening resin composition with other than being combined into and changing as shown in table 1, table 3, with implementation Example 15 has got similarly solidfied material.It should be noted that in the Examples and Comparative Examples of part, as curable resin group The constituent for closing object, instead of the epoxide for being dispersed with rubber particles obtained in Production Example 2 or together in Production Example 2 In the obtained epoxide for being dispersed with rubber particles together, used alicyclic epoxy shown in table 1 or table 3 to close Object.

Wherein, by the hardening resin composition in embodiment 1~16, comparative example 1~24 25 DEG C character (liquid or Solid) it is shown in " character of hardening resin composition " in table 1~3.

Following evaluations are implemented for the solidfied material obtained in Examples and Comparative Examples.

[initial stage reflectivity]

Machining is carried out to the solidfied material obtained in Examples and Comparative Examples, has made long 30mm × wide 30mm × thickness The test film of 3mm.Then, it is surveyed using spectrophotometer (trade name " spectrophotometer UV-2450 ", (strain) Shimadzu Seisakusho Ltd. system) Reflectivity of each test film to the light of wavelength 450nm has been determined (as " initial stage reflectivity ").As a result as shown in table 1~3.

It should be noted that if initial stage reflectivity is 95% or more, it can be said that being special as light reflecting material Excellent.

[the reflectivity conservation rate before and after heat ageing]

Use the test film (solidfied material for the evaluation for having carried out initial stage reflectivity；Long 30mm × wide 30mm × 3mm is thick), by this Test film is put into 120 DEG C of drying machine and carries out after placing experiment (heat resistant test) in 250 hours, in the same manner as initial stage reflectivity Determine the reflectivity of the light of wavelength 450nm.In turn, reflectivity conservation rate has been calculated using following formula (before and after heat ageing). As a result as shown in table 1~3.

[reflectivity conservation rate (before and after heat ageing)]=([reflectivity after heat ageing]/[initial stage reflectivity]) × 100

The reflectivity conservation rate is higher, then shows that the heat resistance of solidfied material is more excellent.It should be noted that adding in 120 DEG C When reflectivity conservation rate of the heat after 250 hours is 90% or more, it may be said that the heat resistance as light reflecting material is especially excellent Different.

[the reflectivity conservation rate before and after ultraviolet ray ageing]

Use the test film (solidfied material for the evaluation for having carried out initial stage reflectivity；Long 30mm × wide 30mm × 3mm is thick), to this Test film is irradiated intensity 10mW/cm²Ultraviolet light experiment in 250 hours (Light Resistance Test) after, it is same as initial stage reflectivity Ground determines the reflectivity of the light of wavelength 450nm.In turn, reflectivity conservation rate has been calculated (before ultraviolet ray ageing using following formula Afterwards).As a result as shown in table 1~3.

[reflectivity conservation rate (before and after ultraviolet ray ageing)]=([reflectivity after ultraviolet ray ageing]/[initial stage reflectivity]) ×100

The reflectivity conservation rate is higher, then shows that the light resistance of solidfied material is more excellent.It should be noted that with intensity 10mW/cm²When reflectivity conservation rate after irradiating 250 hours is 90% or more, it may be said that as the fast light of light reflecting material Property is especially excellent.

[whether there is or not evaluation (obdurability evaluations) for cracking when machining]

Machining is carried out to the solidfied material obtained in Examples and Comparative Examples, has made wide 5mm × long 5mm × thickness The test film of 3mm.The machining of above-mentioned solidfied material has used miniature cutter (trade name " BS-300CL ", Meiwa Forsis (strain) makes), cracking whether is produced when for machining on solidfied material, uses digit microscope (trade name " VHX- 900 ", (strain) Keyence systems) it carried out observation, confirmed.In table 1~3, as evaluation result, show for 1 sample The number [a/10] for the test film that cracking occurs wherein has been confirmed when making 10 test films.

[whether there is or not evaluation (obdurability evaluations) for cracking when reflux]

For the test film as obtained from above-mentioned machining (wide 5mm × long 5mm × thickness 3mm), reflow ovens (quotient is used The name of an article " UNI-5016F ", Nippon Antom (strain) systems), implement 5 seconds, total regurgitant time for maximum temperature with 260 DEG C For 90 seconds reflow treatments.Thereafter, aobvious using number for whether producing cracking on test film by the reflow treatment Micro mirror (trade name " VHX-900 ", (strain) Keyence systems) has carried out observation, has confirmed.In table 1~3, as evaluation result, show The number for the test film that cracking occurs wherein has been confirmed when having gone out the reflow treatment for 1 sample 10 test film of progress [a/10].

[comprehensive judgement]

It is respectively testing as a result, the case where meeting in following (1)~(5) whole items, is determined as zero (good).On the other hand, The case where Arbitrary Term that will be unsatisfactory in following (1)~(5), is determined as × (bad).

(1) initial stage reflectivity：Light reflectivity is 95% or more

(2) the reflectivity conservation rate before and after heat ageing：Reflectivity conservation rate is 90% or more

(3) the reflectivity conservation rate before and after ultraviolet ray ageing：Reflectivity conservation rate is 90% or more

(4) whether there is or not evaluations for cracking when machining：The number to be cracked is 0

(5) whether there is or not evaluations for cracking when flowing back：The number to be cracked is 0

As a result shown in table 1~3 in " comprehensive judgement " column.

It should be noted that about ingredient shown in table 1~3, it is described below.

(epoxide for being dispersed with rubber particles)

What is obtained in Production Example 2 is dispersed with the epoxide of rubber particles

(epoxide)

CELLOXIDE 2021P：Trade name " CELLOXIDE 2021P " (3,4- epoxycyclohexyl-methyls (3,4- epoxies) Naphthenic acid ester), (strain) Daicel systems

EHPE3150：Trade name " EHPE3150 " (1,2- epoxies -4- (the 2- epoxies of bis- (the hydroxymethyl)-n-butyl alcohols of 2,2- Ethyl group) hexamethylene addition product), (strain) Daicel systems

(isocyanuric acid derivative)

TEPIC：Trade name " TEPIC " [triglycidyl group isocyanuric acid ester], Nissan Chemical Industries (strain) system

MA-DGIC：Trade name " MA-DGIC " [monoallyl diglycidyl isocyanuric acid ester], four countries' chemical conversion industry (strain) makes

DA-MGIC：Trade name " DA-MGIC " [diallyl list glycidyl isocyanurate], four countries' chemical conversion industry (strain) makes

(silicone derivative)

X-40-2678：Trade name " X-40-2678 " (intramolecular has the silicone derivative of 2 epoxy groups), SHIN-ETSU HANTOTAI Learn industrial (strain) system

X-40-2720：Trade name " X-40-2720 " (intramolecular has the silicone derivative of 3 epoxy groups), SHIN-ETSU HANTOTAI Learn industrial (strain) system

X-40-2670：Trade name " X-40-2670 " (intramolecular has the silicone derivative of 4 epoxy groups), SHIN-ETSU HANTOTAI Learn industrial (strain) system

(curing agent composition)

MH-700：Trade name " RIKACID MH-700 " (4- methylhexahydrophthalic anhydrides/hexahydrophthalic acid Acid anhydride), new Japan Chemical (strain) system

18X：Trade name " U-CAT 18X " (curing accelerator), San-Apro (strain) systems

(additive)

Ethylene glycol：Trade name " ETHYLENE GLYCOL " and Wako Pure Chemical Industries (strain) system

(curing catalysts)

San Aid SI-100L：Trade name " San Aid SI-100L ", three new chemical industry (strain) systems

(white pigment)

DCF-T-17050：Trade name " DCF-T-17050 " (titanium oxide, 0.3 μm of average grain diameter, 1 μm of maximum particle diameter with Under), Resino Color Industry (strain) system

(inorganic filler)

FB-970FD：Trade name " FB-970FD " (silica, non-surface treated, 16.7 μm of average grain diameter, maximum grain 70 μm of diameter), Denka (strain) system

DAW-1025：Trade name " DAW-1025 " (aluminium oxide, 7.9 μm of average grain diameter, 32 μm of maximum particle diameter), Denka (strain) makes

HF-05：Trade name " HF-05 " (nitriding and oxidizing aluminium, 5 μm of average grain diameter, 5 μm of maximum particle diameter), Denka (strain) systems

Industrial applicibility

The hardening resin composition of the present invention due to above-mentioned composition, being formed with high light reflectivity and Heat resistance and excellent in light-resistance, be not susceptible to light reflective through when the solidfied material that reduces, especially by by compression forming Said effect can be significantly played when forming solidfied material.Thus, it is possible to provide be not susceptible to the brightness of light through when reduce, it is reliable The high optical semiconductor device of property.

Symbol description

100：White reflector

101：Metal wiring (electrode)

102：The carrying region of optical semiconductor

103：Package substrate

104：Closing line

105：The sealing material of optical semiconductor

106：Chip welds (die bonding) material

107：Optical semiconductor

108：Radiating piece

109：Cathode mark

Claims

1. a kind of light reflection hardening resin composition contains cycloaliphatic epoxy (A), rubber particles (B), white Pigment (C), inorganic filler (D), intramolecular have the isocyanuric acid derivative (H) and intramolecular of 1 or more oxirane ring Silicone derivative (I) with 2 or more epoxy groups, and further contain curing agent (E) and curing accelerator (F) or solid Change catalyst (G),

Light reflection curable resin combination is liquid at 25 DEG C.

2. light reflection hardening resin composition according to claim 1, wherein the rubber particles (B) include with (methyl) acrylate has hydroxyl and/or carboxyl for the polymer of necessary monomer component, surface, the rubber particles (B) Average grain diameter is 10~500nm, maximum particle diameter is 50~1000nm.

3. light reflection hardening resin composition according to claim 1 or 2, wherein the alicyclic epoxy closes Object (A) includes following formula (I-1) compound represented：

4. light reflection hardening resin composition described in any one of claim 1 to 3, wherein the isocyanide urea Acid derivative (H) is following formula (III-1) compound represented：

In formula (III-1), R⁷And R⁸It is identical or different, indicate hydrogen atom or the alkyl of carbon atom number 1~8.

5. light reflection hardening resin composition according to any one of claims 1 to 4, wherein the white face Expect that (C) is selected from least one of titanium oxide, zirconium oxide, zinc oxide and barium sulfate, the inorganic filler (D) is selected from two At least one of silica, aluminium oxide, silicon nitride, aluminium nitride and boron nitride.

6. light reflection hardening resin composition according to any one of claims 1 to 5, used for transfer molding or Compression forming resin combination.

7. according to light reflection hardening resin composition according to any one of claims 1 to 6, is formed and used for reflector Resin combination.

8. a kind of solidfied material is the solidification of light reflection hardening resin composition according to any one of claims 1 to 7 Object.

9. a kind of optical semiconductor device, at least has：

Optical semiconductor and

The reflector formed by the solidfied material of light reflection hardening resin composition according to any one of claims 8.