CN110229524A - Light reflecting material curability silicon-ketone composition, silicone resin solidfied material, reflector and LED matrix - Google Patents
Light reflecting material curability silicon-ketone composition, silicone resin solidfied material, reflector and LED matrix Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The present invention, which provides one kind, has high fluidity, generate heat resistance (thermal stability), particularly resistance to thermochromism is excellent and can get the light reflecting material of the solidfied material of higher light reflectivity curability silicon-ketone composition.The light reflecting material curability silicon-ketone composition is characterized in that, contain: (A-1) of 30~70 mass parts: (a) the addition reaction product with the polycycle hydrocarbon with 2 addition reactivity carbon-carbon double bonds in 2 compounds and (b) molecule with the hydrogen atom of silicon atom bonding in a molecule represented by general formula (1) has at least two addition reactivity carbon-carbon double bond in a molecule；(A-2) of 30~70 mass parts: compound represented by general formula (3)；(B) organo-silicon compound in a molecule with 3 or more with the hydrogen atom of silicon atom bonding；(C) hydrosilylation reaction catalyst；(D) titanium dioxide powder；And (E) fumed silica powder.
Description
Technical field
The present invention relates to generate as light reflecting material, particularly use reflection equipment as White LED (light emitting diode)
Expect the light reflecting material curability silicon-ketone composition (white Thermocurable silicon-ketone composition) of useful silicone resin solidfied material, be somebody's turn to do
The solidfied material of composition and the reflector and LED matrix for having used the solidfied material.
Background technique
It is in recent years, excellent with high efficiency light-emitting and drive characteristic or lighting repeat property due to optical semiconductors such as LED,
Therefore extensive utilization has been obtained as indicator or light source.Especially backlight or photograph of the White LED as display device
The flash lamp of machine and be widely used, in addition, as follow-on lighting device also by expectation.In order to improve direction of illumination
Light extraction efficiency is mounted with the component (hereinafter referred to as reflector) for reflecting issued light in such light emitting device.
Now, as the material (hereinafter referred to as reflector material) for reflector, polyphthalamide resin is obtained
Extensive utilization.However, polyphthalamide resin is easy to happen the deterioration caused by being used for a long time, especially changes colour, shells
From, mechanical strength decline etc., it is difficult to be suitable for high output light emitting element of today.
In order to solve the problems, it is proposed in Patent Documents 1 to 4 a kind of with epoxy resin or silicone and metal oxidation
Object etc. is the reflector material of constituent, in addition, proposing a kind of ceramic reflectors material in patent document 5.However, this
Although a little solid materials have excellent heat resistance, mechanical property, lack mobility at room temperature, therefore exist at the time of molding
Need the problem in the operational workability such as high temperature.Further, since these solid materials also lack mobility at high temperature, because
There is also be difficult to form the technologic problems such as the fine structural body of structural body or large area for this.
Existing technical literature
Patent document
Patent document 1: No. 2656336 bulletins of Japan Patent
Patent document 2: Japanese Unexamined Patent Publication 2008-106226 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2008-189833 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2013-221075 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2008-117932 bulletin
Summary of the invention
The technical problem to be solved in the present invention
Present invention is made in view of the above circumstances, provides a kind of heat-resisting with high fluidity, generation at room temperature
Property (thermal stability), particularly resistance to thermochromism are excellent and can get the light reflecting material of the solidfied material of higher light reflectivity
With curability silicon-ketone composition.That is, the purpose of the present invention is to provide generate as light reflecting material, particularly as white
The light reflecting material of the useful silicone resin solidfied material of LED reflector material is with curability silicon-ketone composition and by the composition
Solidfied material formed reflector (especially white light-emitting diode use).
Solve the technological means of technical problem
In order to reach above-mentioned technical problem, the present invention provides a kind of light reflecting material curability silicon-ketone composition, contains
Have:
(A-1) of 30~70 mass parts: (a) there is 2 and silicon atom bonding in a molecule represented by the following general formula (1)
Hydrogen atom compound and (b) molecule in the polycycle hydrocarbon with 2 addition reactivity carbon-carbon double bonds addition reaction it is raw
At object, which has at least two addition reactivity carbon-carbon double bond in a molecule；
(A-2) of 30~70 mass parts: compound represented by the following general formula (3) (wherein, described (A-1) ingredient and institute
That states (A-2) ingredient adds up to 100 mass parts)；
(B) have the organo-silicon compound of the hydrogen atom of 3 or more and silicon atom bonding (relative to composition in a molecule
In addition reactivity carbon-carbon double bond, in composition with the total amount of the hydrogen atom of silicon atom bonding with molar ratio computing for 0.5
~3.0 amount)；
(C) hydrosilylation reaction catalyst；
(D) titanium dioxide powder；And
(E) fumed silica powder.
[chemical formula 1]
In formula, A is the bivalent group in the group being made of the group represented by the following general formula (2), R1It independently is
The alkoxy that the monovalent hydrocarbon or carbon atom number that carbon atom number that is unsubstituted or replacing is 1~12 are 1~6.
[chemical formula 2]
[chemical formula 3]
In formula, Ph is phenyl, R2It independently is the monovalent hydrocarbon that carbon atom number that is unsubstituted or replacing is 1~12, R3For
The group of the carbon-carbon double bond containing addition reactivity, the integer that n is 1~20.
If such light reflecting material curability silicon-ketone composition, then there is high fluidity, Neng Gousheng at room temperature
It is excellent at heat resistance (thermal stability), particularly resistance to thermochromism and can get the solidfied material of higher light reflectivity.
Furthermore it is preferred that (b) is indicated by the following general formula (4).
[chemical formula 4]
In formula, R4The alkenyl for being 2~12 for unsubstituted or substituted carbon atom number.
Furthermore it is preferred that (b) is two ring of 5- vinyl [2.2.1] hept-2-ene", 6- vinyl two rings [2.2.1] hept- 2-
Any one in alkene and their combination.
If such raw material (b), then intensity more effectively can be assigned to solidfied material, high rigidity is made.
Furthermore it is preferred that (B) ingredient is silicone compounds represented by the following general formula (5).
[chemical formula 5]
In formula, R5Independently being hydrogen atom or the carbon atom number that is unsubstituted or replacing in addition to alkenyl is 1~12
Monovalent hydrocarbon, R6For methyl or hydrogen atom, the integer that p is 1~10, the integer that q is 0~7.Mark the siloxane unit and mark of p
The siloxane unit of note q is arranged in a manner of random mutually.
If such (B) ingredient, then as reflector material in use, can obtain that there is abundant mechanical property
Solidfied material.
At this point, it is preferred that viscosity at 25 DEG C is 5~500Pas.
If such viscosity, then mobility is high, and operational workability becomes more excellent.
In addition, the present invention provides a kind of light reflecting material silicone resin solidfied material, by above-mentioned light reflecting material
It formed with curability silicon-ketone composition, solidified and obtained.
It is if such light reflecting material silicone resin solidfied material, then applicable to make reflector material.
At this point, it is preferred that the reflectivity for just completing the light of 430~800nm of wavelength after solidifying is 95% or more, in 170 DEG C of rings
The reflectivity of the light of 430~800nm of wavelength under border after exposure 1000 hours is 82% or more.
It is if such light reflecting material silicone resin solidfied material, then applicable to be difficult to happen as caused by being used for a long time
Deterioration, particularly discoloration, removing, mechanical strength decline etc. reflector material.
In addition, at this point, it is preferred that shore D hardness is 65 or more.
If such shore D hardness, then becomes as the solidfied material of reflector material and be more suitable for carrying out using scribing machine
The hardness cut off and be sliced.
In addition, the present invention provides a kind of reflector, formed by above-mentioned light reflecting material with silicone resin solidfied material.
Further, the present invention provides a kind of LED matrix, is mounted with above-mentioned reflector.
It, then can be after maintaining higher light extraction efficiency during length if such reflector or LED matrix.
Invention effect
Light reflecting material curability silicon-ketone composition of the invention has high fluidity, therefore workability at room temperature
Operability is excellent.In addition, the light reflective properties of light reflecting material silicone resin solidfied material obtained from solidifying above-mentioned composition
Excellent with heat resistance (thermal stability), especially resistance to thermochromism is excellent.Therefore, above-mentioned solidfied material is as light reflecting material, example
Such as used as light emitting device, particularly as the reflector material of White LED be useful.
Specific embodiment
As described above, seek to develop it is a kind of there is high fluidity at room temperature, generate heat resistance (thermal stability), particularly
Resistance to thermochromism is excellent and can get the light reflecting material of the solidfied material of higher light reflectivity curability silicon-ketone composition.
Present inventor conscientiously studies above-mentioned technical problem, as a result, it has been found that, by containing with spy
Determine the heat for the reaction addition product and the organopolysiloxane with specific structure of structure generated by hydrosilylation reactions
Titanium dioxide powder is blended in curability silicon-ketone composition, can obtain having high fluidity, generation heat resistance (hot steady at room temperature
It is qualitative), particularly resistance to thermochromism it is excellent and can get the light reflecting material curability of the solidfied material of higher light reflectivity
Silicon-ketone composition, so as to complete the present invention.
That is, the present invention is a kind of light reflecting material curability silicon-ketone composition, contain:
(A-1) of 30~70 mass parts: (a) there is 2 and silicon atom bonding in a molecule represented by above-mentioned general formula (1)
Hydrogen atom compound and (b) molecule in the polycycle hydrocarbon with 2 addition reactivity carbon-carbon double bonds addition reaction it is raw
At object, which has at least two addition reactivity carbon-carbon double bond in a molecule；
(A-2) of 30~70 mass parts: compound (wherein, described (A-1) ingredient and institute represented by above-mentioned general formula (3)
That states (A-2) ingredient adds up to 100 mass parts)；
(B) have the organo-silicon compound of the hydrogen atom of 3 or more and silicon atom bonding (relative to composition in a molecule
In addition reactivity carbon-carbon double bond, in composition with the total amount of the hydrogen atom of silicon atom bonding with molar ratio computing for 0.5
~3.0 amount)；
(C) hydrosilylation reaction catalyst；
(D) titanium dioxide powder；And
(E) fumed silica powder.
The present invention is described in detail below, but the present invention is not limited thereto.In addition, in the present specification, Me and Ph
Methyl and phenyl are respectively indicated, viscosity is the value using rotary viscosity design determining.
[(A-1) ingredient]
(A-1) ingredient of light reflecting material curability silicon-ketone composition of the invention is to assign to the solidfied material after solidification
Intensity and the ingredient that high rigidity is made.
(A-1) ingredient is the hydrogen atom in a molecule represented by (a) the following general formula (1) with 2 with silicon atom bonding
Compound and (b) molecule in 2 addition reactivity carbon-carbon double bonds polycycle hydrocarbon addition reaction product,
There is at least two addition reactivity carbon-carbon double bond in one molecule.Below to the raw material (a) and original of the raw material as (A-1) ingredient
Material (b) is illustrated.
[chemical formula 1]
In formula, A is the bivalent group in the group being made of the group represented by the following general formula (2), R1It independently is
The alkoxy that the monovalent hydrocarbon or carbon atom number that carbon atom number that is unsubstituted or replacing is 1~12 are 1~6.
[chemical formula 2]
< raw material (a) >
In a molecule as represented by the reaction raw materials as (A-1) ingredient, (a) above-mentioned general formula (1) have 2 with
In the compound (raw material (a)) for the hydrogen atom (hereinafter, sometimes referred to as " SiH ") that silicon atom combines, the A in above-mentioned general formula (1) is
Bivalent group represented by above-mentioned general formula (2), therefore it is compound represented by the following general formula (6),
[chemical formula 6]
R1It independently is the monovalent hydrocarbon that unsubstituted or substituted carbon atom number is 1~12 or the alkane that carbon atom number is 1~6
Oxygroup, preferably independently for unsubstituted or substituted carbon atom number be 1~6 monovalent hydrocarbon or carbon atom number be 1~6 alcoxyl
Base.
In above-mentioned general formula (6), work as R1When for monovalent hydrocarbon, such as methyl, ethyl, propyl, isopropyl, fourth can be enumerated
The alkyl such as base, tert-butyl, amyl, isopentyl, hexyl, Sec-Hexyl；The naphthenic base such as cyclopenta, cyclohexyl；Phenyl, o-tolyl,
Between the aryl such as tolyl, p-methylphenyl；The aralkyl such as benzyl, 2- phenylethyl；Vinyl, allyl, 1- cyclobutenyl, 1- hexene
The alkenyls such as base；To alkenyl aryls such as ethenylphenyls；And the hydrogen atom with 1 or more of the carbon atom bonding in these groups
Made of the substitution such as halogen atom, cyano, cyclic group containing epoxy, the halogen such as chloromethyl, 3- chloropropyl, 3,3,3- trifluoro propyl
Change alkyl；2- cyanoethyl；3- glycidoxypropyl group etc..
In addition, working as R1When for alkoxy, for example, can enumerate methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy,
Sec-butoxy, tert-butoxy etc..
Among above-mentioned, R1Group preferably in addition to alkenyl and alkenyl aryl, due to R all in a molecule1For methyl
Compound be industrially easy preparation, be easy to get, so particularly preferably.
As compound represented by the above-mentioned general formula (6), such as structural formula can be enumerated: HMe2Si-p-C6H4-
SiMe2Bis- (dimetylsilyl) benzene of 1,4- represented by H, structural formula: HMe2Si-m-C6H4-SiMe21,3- represented by H
Bis- (dimetylsilyl) benzene, structural formula: HMe2Si-o-C6H4-SiMe21,2- represented by H bis- (dimetylsilyls)
The silicon such as benzene phenylene (silphenylene) compound.
In addition, compound (the above-mentioned raw materials of the reaction raw materials as (A-1) ingredient represented by the above-mentioned general formula (6)
(a)) can be used alone one kind, also can be used in combination two or more.
< raw material (b) >
There is the polycyclic of 2 addition reactivity carbon-carbon double bonds in (b) molecule of the reaction raw materials as (A-1) ingredient
In formula hydrocarbon (raw material (b)), " addition reactivity " is to refer to receive the addition with the hydrogen atom of silicon atom bonding (as silane
Alkylation reaction and it is known that) property.
In addition, raw material (b) be it is following any one: (i) formed polycycle hydrocarbon polycyclic skeleton carbon atom in,
The compound of addition reactivity carbon-carbon double bond is formed between 2 adjacent carbon atoms；(ii) more with formation polycycle hydrocarbon
Compound made of the hydrogen atom of the carbon atom bonding of ring skeleton is replaced by the group of the carbon-carbon double bond containing addition reactivity；Or
(iii) in the carbon atom of polycyclic skeleton for forming polycycle hydrocarbon, addition reactivity is formed between 2 adjacent carbon atoms
Carbon-carbon double bond, and it is double by the carbon of carbon containing addition reactivity with the hydrogen atom of the carbon atom bonding for the polycyclic skeleton for forming polycycle hydrocarbon
Compound made of the group of key replaces.Herein, as the group of the carbon-carbon double bond containing addition reactivity, such as ethylene can be enumerated
The group etc. that the alkenyls such as base, allyl, acrylic, cyclobutenyl, hexenyl, norborny, especially carbon atom number are 2~12.
As (b) ingredient, such as alkenyl norbornene compound represented by the following general formula (4) can be enumerated.Into one
Step, as the concrete example of compound represented by the following general formula (4), can enumerate 5- ethylene represented by following structural formula (7)
Two ring of 6- vinyl [2.2.1] hept-2-ene" and the two represented by two ring of base [2.2.1] hept-2-ene", following structural formula (8)
Combination (hereinafter, when not needing to distinguish this three, sometime collectively referred to as " vinyl norbornene ").
[chemical formula 4]
In formula, R4The alkenyl for being 2~12 for unsubstituted or substituted carbon atom number.
[chemical formula 7]
[chemical formula 8]
In addition, the position of substitution of the vinyl of above-mentioned vinyl norbornene can be it is cis- configuration it is (exo shape) or trans-
Configure any one in (endo shape), in addition, such configuration it is different raw material (b) in terms of do not cause spy
Other difference, therefore may be the combination of the isomers of both configurations.
The preparation > of < (A-1) ingredient
(A-1) ingredient of light reflecting material of the invention curability silicon-ketone composition, which can be used as in a molecule, to be had at least
2 addition reactivity carbon-carbon double bonds and without SiH addition reaction product and obtain, by anti-in hydrosilylation
In the presence of answering catalyst, the above-mentioned raw materials (a) in 1 mole of a molecule with 2 SiH is made to rub with more than 1 mole and for 10
Below you, it is preferably greater than 1 mole and for there are 2 addition reactivity carbon-carbon double bonds in 5 moles of excessive molecules below
Above-mentioned raw materials (b) carry out addition reaction and obtain.
(A-1) ingredient obtained through the above way is other than the addition reactivity carbon-carbon double bond from raw material (b), also
(for specific, the R in self-drifting (1) can be carried out containing raw material (a) is come from1) addition reactivity carbon-carbon double bond, therefore
Containing at least two addition reactivity carbon-carbon double bond in one molecule, quantity is preferably 2~6, and more preferably 2.If addition is anti-
Answering property carbon-carbon double bond is such quantity, then obtained from solidifying light reflecting material of the invention with curability silicon-ketone composition
Solidfied material will not become fragile.
As above-mentioned hydrosilylation reaction catalyst, all known catalyst can be used.Such as it can enumerate
It is supported with reaction product, platinum and the divinyl of the carbon dust of platinum, platinum black, platinum chloride, chloroplatinic acid, chloroplatinic acid and monohydric alcohol
The complex compound of the vinylsiloxanes such as base tetramethyl disiloxane；The complex compound of chloroplatinic acid and olefines, bis- (acetoacetate) platinum
Etc. platinum-type catalysts；The platinums group metal class catalyst such as palladium class catalyst, rhodium class catalyst.In addition, addition reaction condition, solvent
It uses etc. and to be not particularly limited, as long as with usually identical.
As described above, in the preparation of (A-1) ingredient, due to using the upper of excess molar amounts relative to above-mentioned raw materials (a)
Raw material (b) is stated, therefore addition reactivity carbon carbon of (A-1) ingredient with 2 structures from above-mentioned raw materials (b) in a molecule
Double bond.Further, (A-1) ingredient has the residue from above-mentioned raw materials (a), which can be containing by coming from above-mentioned raw materials
(b) structure made of the bonding of the residue of divalent of structure but the polycycle hydrocarbon without addition reactivity carbon-carbon double bond.
That is, as (A-1) ingredient, such as compound represented by the following general formula (9) can be enumerated.
[chemical formula 9]
Y-X-(Y′-X)m-Y (9)
In formula, X is the residue of divalent of the compound of above-mentioned raw materials (a), and Y is the monovalence of the polycycle hydrocarbon of above-mentioned raw materials (b)
Residue, Y ' are the residue of divalent of above-mentioned raw materials (b), the integer that m is 0~10, preferably 0~5 integer.
In addition, for the m value of the quantity as repetitive unit represented by above-mentioned (Y '-X), can by adjusting with 1 mole
Above-mentioned raw materials (b) reaction above-mentioned raw materials (a) excessive mole and set.
As the Y in above-mentioned general formula (9), specifically, can for example enumerate monovalence residue represented by following structural formula
(hereinafter, they are referred to as " NB yl " when not needing to distinguish following 6 kinds of residues, in addition, sometimes also not to the knot of 6 kinds of residues
Structure is distinguished and is abbreviated as " NB ").
As the Y ' in above-mentioned general formula (9), specifically, it is residual for example to enumerate divalent represented by following structural formula
Base.
Wherein, the left and right directions of asymmetric residue of divalent represented by structure above is not limited to remember as described above
It carries, structure above, which is substantially included on paper, rotates structure made of 180 degree for each above structure.
The preferred concrete example of (A-1) ingredient represented by above-mentioned general formula (9) described below, but it is not limited to this (in addition,
The meaning of " NB " is as described above).
In formula, r be 0~10 integer.
Further, (A-1) ingredient of light reflecting material of the invention curability silicon-ketone composition can be used alone one kind,
Also it can be used in combination two or more.
[(A-2) ingredient]
(A-2) compatibility of ingredient and (A-1) ingredient is high, and the intensity of the solidfied material after solidifying will not be made to decline, to assign
The ingredient of heat resistance (thermal stability), particularly resistance to thermochromism.
(A-2) ingredient is the diorganopolysiloxanecompositions of straight-chain, and main chain is made of the repetition of diphenylsiloxane unit,
Two end of strand is blocked by three organosiloxies of the group with the carbon-carbon double bond containing addition reactivity.(A-2) ingredient has
Machine polysiloxanes can be used alone one kind, also can be used simultaneously molecular weight, with type of organic group of silicon atom bonding etc. no
Same two or more organopolysiloxanes.
As the R in above-mentioned general formula (3)3The carbon-carbon double bond containing addition reactivity group and above-mentioned < raw material (b) >
It is documented identical in explanation, for containing have can receive the addition with the hydrogen atom of silicon atom bonding (as hydrosilanes
Change reaction and it is known that) property carbon-carbon double bond group.
The group of the above-mentioned carbon-carbon double bond containing addition reactivity can be used alone one kind, also can be used in combination two or more.
The concrete example of group as the above-mentioned carbon-carbon double bond containing addition reactivity, can enumerate vinyl, allyl, 5- oneself
The carbon atom numbers such as alkenyl, acrylic, cyclobutenyl are the alkenyl of 2~20, preferably 2~10；The carbon atom numbers such as 1,3- butadienyl
For 4~10 alkane dialkylene；Acryloxy (- O (O) CCH=CH2), methacryloxy (- O (O) CC (CH3)=CH2)
Etc. the combination of above-mentioned alkenyl and carbonyl oxygroup；Acrylamido (- NH (O) CCH=CH2) etc. above-mentioned alkenyl and carbonylamino group
It closes.
Wherein, from when obtaining the raw material of (A-2) ingredient productivity and cost and (A-2) ingredient reactivity angularly
It sets out, as the group of the above-mentioned carbon-carbon double bond containing addition reactivity, preferred vinyl, allyl and 5- hexenyl, particularly preferably
Vinyl.
R in above-mentioned general formula (3)2It independently is the monovalent hydrocarbon that carbon atom number that is unsubstituted or replacing is 1~12, example
Methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, amyl, isopentyl, hexyl, Sec-Hexyl alkyl can such as be enumerated；Ring
The naphthenic base such as amyl, cyclohexyl；The aryl such as phenyl, o-tolyl, tolyl, p-methylphenyl；The virtues such as benzyl, 2- phenylethyl
Alkyl；The alkenyls such as vinyl, allyl, 1- cyclobutenyl, 1- hexenyl；To alkenyl aryls such as ethenylphenyls；And and these
1 or more hydrogen atom of the carbon atom bonding in group is made of the substitution such as halogen atom, cyano, cyclic group containing epoxy, example
Such as chloromethyl, 3- chloropropyl, 3,3,3- trifluoro propyl halogenated alkyl；2- cyanoethyl；3- glycidoxypropyl group etc..
Among above-mentioned, due to R2It is industrially easy preparation for the compound of methyl or phenyl, is easy to get, so especially
It is preferred that.
In (A-2) ingredient, the polymerization degree n of diphenylsiloxane unit is 1~20, preferably 1~15, further preferably
It is 2~10.If n is greater than 20, the decline of mobility or the decline with the compatibility of (A-1) ingredient can be caused, so not preferably.
Relative to total 100 mass parts of (A-1) ingredient and (A-2) ingredient, the blended amount of (A-2) ingredient is 30~70 matter
Measure part, preferably 35~65 mass parts, further preferably 40~60 mass parts.If the blended amount of (A-2) ingredient is less than 30 matter
Part is measured, then resistance to thermochromism decline, if the intensity of solidfied material, especially hardness decline more than 70 mass parts.
(A-2) ingredient can for example obtain in the following manner: make dichloro base silane or dialkoxy diphenyl silicon
The two degree of functionality silane such as alkane is hydrolyzed after condensation or while condensation is hydrolyzed, and contains addition reaction using having
The end-capping reagent of the group of property carbon-carbon double bond blocks end.
[(B) ingredient]
(B) ingredient of light reflecting material curability silicon-ketone composition of the invention is to have 3 or more SiH in a molecule
Organo-silicon compound.The SiH in (B) ingredient is somebody's turn to do by hydrosilylation reactions and above-mentioned (A-1) and (A-2) ingredient one
Possessed at least two addition reactivity carbon-carbon double bond carries out addition in molecule, to generate the solidfied material of space network.
As such (B) ingredient, such as silicone compounds represented by the following general formula (5) can be enumerated.
[chemical formula 5]
In formula, R5Independently being hydrogen atom or the carbon atom number that is unsubstituted or replacing in addition to alkenyl is 1~12
Monovalent hydrocarbon, R6For methyl or hydrogen atom, the integer that p is 1~10, the integer that q is 0~7.Mark the siloxane unit and mark of p
The siloxane unit of note q is arranged in a manner of random mutually.
As the R in above-mentioned general formula (5)5, such as can enumerate methyl, ethyl, propyl, isopropyl, butyl, tert-butyl,
The alkyl such as amyl, isopentyl, hexyl, Sec-Hexyl；The naphthenic base such as cyclopenta, cyclohexyl；It is phenyl, o-tolyl, tolyl, right
The aryl such as tolyl；The aralkyl such as benzyl, 2- phenylethyl；To alkenyl aryls such as ethenylphenyls；And in these groups
Carbon atom bonding 1 or more hydrogen atom by halogen atom, cyano, cyclic group containing epoxy etc. replace made of, such as chloromethane
The halogenated alkyls such as base, 3- chloropropyl, 3,3,3- trifluoro propyl；2- cyanoethyl；3- glycidoxypropyl group etc..
Among above-mentioned, due to R5It is industrially easy preparation for the compound of methyl or phenyl, is easy to get, so especially
It is preferred that.
The preferred concrete example of above-mentioned (B) ingredient described below, but it is not limited to this.
HMe2SiO(HMeSiO)2(Ph2SiO)2SiMe2H
HMe2SiO(HMeSiO)2(Ph2SiO)2(Me2SiO)2SiMe2H
HMe2SiO(HMeSiO)1(Ph2SiO)1(Me2SiO)4SiMe2H
HMe2SiO(HMeSiO)3(Me2SiO)5SiMe2H
(B) ingredient of light reflecting material of the invention curability silicon-ketone composition can be used alone one kind, can also combine
Using two or more.
(B) blended amount of ingredient is preferably set in the following manner.Light reflecting material of the invention curability silicone
Composition containing the ingredient (for example, (G) ingredient described hereinafter) except (B) ingredient in addition to SiH and remove (A-1) or
(A-2) having with the ingredient of the addition reactivity carbon-carbon double bond of silicon atom bonding (for example, foring and platinum other than ingredient
In the state of complex compound, vinylsiloxane in the present compositions can be included in a manner of (C) ingredient described hereinafter) in
Any one or two kinds.Accordingly, with respect to double with the addition reactivity carbon carbon of silicon atom bonding in 1 mole this composition
Key, in this composition is preferably 0.5~3.0 mole with the amount of the hydrogen atom of silicon atom bonding, and more preferably 0.8~2.0 rubs
You.If the blended amount of (B) ingredient is that the amount of the such condition of satisfaction can be by of the invention when being used as reflector material
Light reflecting material obtains the solidfied material with sufficient mechanical property with curability silicon-ketone composition.
Have in only (A-1) and (A-2) ingredient with the addition reactivity carbon-carbon double bond of silicon atom bonding and only (B) ingredient
When with SiH, preferably (B) ingredient is set as making in light reflecting material of the invention with the blended amount in curability silicon-ketone composition
It is 0.5~3.0 mole relative to the SiH in (B) ingredient of the addition reactivity carbon-carbon double bond in 1 mole of above-mentioned (A) ingredient
Amount, be more preferably set as in (B) ingredient for making the addition reactivity carbon-carbon double bond in above-mentioned (A) ingredient relative to 1 mole
The amount that SiH is 0.8~2.0 mole.
[(C) ingredient]
The hydrosilylation reactions of (C) ingredient as light reflecting material of the invention curability silicon-ketone composition are catalyzed
Known all catalyst can be used in agent.Such as the carbon dust for being supported with platinum, platinum black, platinum chloride, chlorine can be enumerated
The network of the vinylsiloxanes such as platinic acid, the reaction product of chloroplatinic acid and monohydric alcohol, platinum and divinyl tetramethyl disiloxane
Close object；The platinum-type catalysts such as the complex compound of chloroplatinic acid and olefines, bis- (acetoacetate) platinum；Palladium class catalyst, rhodium class catalyst
Equal platinums group metal class catalyst.
(C) as long as ingredient uses the blended amount in curability silicon-ketone composition as catalysis in light reflecting material of the invention
The effective quantity of agent, is not particularly limited, relative to the total of above-mentioned (A-1), (A-2) and (B) ingredient, with platinum group metal original
The quality criteria meter of son preferably is blended with (C) ingredient of 1~500ppm, the amount for particularly preferably blending 2~100ppm or so.
By the blended amount in the range that is set as such, the time needed for capable of making curing reaction becomes appropriateness, will not generate solidification
The problems such as object colours.
(C) ingredient can be used alone one kind, also can be used in combination two or more.
[(D) ingredient]
(D) ingredient of light reflecting material curability silicon-ketone composition of the invention is titanium dioxide powder.Due to (D) ingredient
Titanium dioxide powder (metal compound powders) be white, therefore by blend (D) ingredient, light reflecting material silicon of the invention
Resin cured matter shows good light reflectivity.
(D) partial size of ingredient is not particularly limited, and as (D) ingredient, usually commercially available average grain diameter is 0.1~200 μ mostly
The substance of the range of m and its easy to operate, substance of more preferable 0.5~100 μm of range.If the average grain diameter of (D) ingredient is
0.1~200 μm of range, then light reflecting material of the invention is easy to become good with the mobility of curability silicon-ketone composition,
In addition, the surface of the solidfied material of composition is not easy roughening, light reflective properties effectively improve.In addition, in the present specification,
Average grain diameter refers to be equivalent to cumulative distribution 50% found out by using the particle size distribution device of laser diffractometry
Volume reference average grain diameter.
Relative to total 100 mass parts of above-mentioned (A-1), (A-2) and (B) ingredient, the blended amount of (D) ingredient is preferably 50
~1000 mass parts, more preferably 60~900 mass parts are even more preferably 100~800 mass parts.If blended amount is 50
In the range of~1000 mass parts, then light reflecting material of the invention is easy to become good with the mobility of curability silicon-ketone composition
It is good, in addition, the light reflective properties of the solidfied material of composition are easy to become abundant.
(D) ingredient also can be used in combination two or more.
[(E) ingredient]
(E) ingredient of light reflecting material curability silicon-ketone composition of the invention is fumed silica powder.It is logical
Cross in the composition (D) ingredient that specific gravity can be prevented comprising (E) ingredient to be greater than (A-1), (A-2) and (B) ingredient precipitating,
Cohesion obtains not uneven solidfied material.
(E) partial size of ingredient is not particularly limited, and as (E) ingredient, usually commercially available average grain diameter is 1~100nm mostly
Range substance and its easy to operate, substance of the range of more preferable 5~50nm.The average grain diameter of (if E) ingredient 1~
In the range of 100nm, then precipitating, the cohesion of (D) ingredient can be more efficiently prevented from, not uneven solidfied material is obtained.
Relative to total 100 mass parts of above-mentioned (A-1), (A-2) and (B) ingredient, the blended amount of (E) ingredient is preferably 1
~50 mass parts, more preferably 1~20 mass parts are even more preferably 1~10 mass parts.If blended amount be 50 mass parts with
Under, then light reflecting material of the invention shows more good mobility with curability silicon-ketone composition, if 1 mass parts with
On, then it will not cause the precipitating or cohesion of (D) ingredient.
(E) ingredient also can be used in combination two or more.
Furthermore it is preferred that in light reflecting material of the invention blending adhesiveness modifier in curability silicon-ketone composition.Make
For adhesiveness modifier, silane coupling agent or its oligomer can be exemplified, there is reactive group identical with silane coupling agent
Silicone etc., wherein preferred following (F) ingredients and (G) ingredient.
(F) ingredient is compound represented by the following general formula (10), and (G) ingredient is chemical combination represented by the following general formula (11)
Object.
[chemical formula 10]
In formula, the integer that s is 1~3, the integer that t is 0~2, wherein s+t 3.It marks the amide units of s and marks t's
Amide units are arranged in a manner of random mutually.
[chemical formula 11]
In formula, the integer that u is 1~2, the integer that v is 2~4, wherein the integer that u+v is 4~5.Mark the siloxanes list of u
Member and the siloxane unit of mark v are arranged in a manner of random mutually.
(F) ingredient and (G) ingredient are to improve light reflecting material of the invention curability silicon-ketone composition and its consolidate
Compound blends any ingredient in composition to the adhesiveness of substrate.Herein, substrate refers to the metal materials such as gold, silver, copper, nickel
The high molecular materials such as the ceramic materials such as material, aluminium oxide, aluminium nitride, titanium oxide, silicone resin, epoxy resin.(F) ingredient and (G) at
Divide the one kind that respectively can be used alone, also can be used in combination two or more.
Relative to total 100 mass parts of above-mentioned (A-1), (A-2) and (B) ingredient, (F) ingredient and (G) ingredient are respective
Blended amount is preferably 1~30 mass parts, more preferably 5~20 mass parts.If blended amount is 1~30 mass parts, of the invention
Light reflecting material curability silicon-ketone composition and its solidfied material are effectively improved the adhesiveness of substrate, and are not easy
Color.
As the preferred concrete example of (F) ingredient, compound represented by following formula can be enumerated, but it is not limited to this.
As the preferred concrete example of (G) ingredient, compound represented by following formula can be enumerated, but it is not limited to this.
[other blend ingredient]
In addition to the above ingredients, if blend other in curability silicon-ketone composition to light reflecting material of the invention
Ingredient is arbitrary.As other compositions, such as ingredient described below can be enumerated.
< antioxidant >
There are the addition reactivity carbon-carbon double bonds in above-mentioned (A-1) ingredient to remain in light of the invention with unreacted state
Situation in the solidfied material of reflecting material curability silicon-ketone composition, such as there are following situations: containing being present in following knots
2- (two rings [2.2.1] represented by (two rings [2.2.1] hept-2-ene" -5- base) ethyl of 2- represented by structure formula and following structural formula
Hept-2-ene" -6- base) ethyl any one or two kinds in carbon-carbon double bond.Moreover, if containing such carbon-carbon double bond,
The reason of being aoxidized because of the oxygen in atmosphere, becoming solidfied material coloring.Therefore, in light reflecting material of the invention curability silicone
In composition, it can prevent from colouring in advance as desired by antioxidant is blended.
2- (two rings [2.2.1] hept-2-ene" -5- base) ethyl
2- (two rings [2.2.1] hept-2-ene" -6- base) ethyl
As the antioxidant, known all antioxidants can be used, such as hindered amine compound can be exemplified
Or hindered phenol compound, specifically, can enumerate 2,6- di-tert-butyl-4-methy phenol, 2,5-, bis- tertiary pentyl hydroquinone,
2,5 di tert butyl hydroquinone, 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol)s, 2,2 '-di-2-ethylhexylphosphine oxides (4- methyl-
6- tert-butyl phenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol)s etc..They can be used alone one kind, can also group
It closes using two or more.
In addition, when using the antioxidant, as long as effective quantity of the blended amount as antioxidant, without spy
It does not limit, relative to the total of above-mentioned (A-1), (A-2) and (B) ingredient, in terms of quality criteria, preferably is blended with 10~10,
000ppm, 100~1,000ppm or so is particularly preferably blended.It, can be abundant by the blended amount in the range that is set as such
Oxidation resistance is played, coloring, oxidative degradation etc. is not generated, obtains the excellent solidfied material of light reflective properties.
Other > of <
In addition, 1- ethynylcyclohexanol, 3,5- dimethyl -1- hexin-can be blended in order to ensure working life (pot life)
The addition reactions controlling agent such as 3- alcohol.
Further, it also can be used for assigning the light stabilizer to the repellence of light deterioration, the light deterioration origin is spontaneous
The luminous energy such as the light and sunlight ray of optical element cause.As the light stabilizer, the free radical generated by photo-oxidative degradation is captured
Hindered amines stabilizer be it is suitable, by using antioxidant simultaneously, antioxidant effect is further improved.As light
The concrete example of stabilizer, can enumerate bis- (2,2,6,6- tetramethyl -4- piperidyl) sebacates, 4- benzoyl -2,2, and 6,6-
Tetramethyl piperidine etc..
[light reflecting material curability silicon-ketone composition]
Light reflecting material of the invention with curability silicon-ketone composition (white Thermocurable silicon-ketone composition) before curing
For liquid, viscosity at 25 DEG C is preferably 5~500Pas, more preferably 10~400Pas.If viscosity 5~
In the range of 500Pas, then the workability operability of the composition obtained is easy to become good, is not easy in forming and hardening
Generate being mixed into for bubble or air.
The viscosity of light reflecting material curability silicon-ketone composition of the invention can by (A-1) (A-2)~(E) ingredient and
Other blend the blending ratio of ingredients, the viscosity of liquid substance in these ingredients and average grain diameter of (D) and (E) ingredient etc.
It is adjusted.
[light reflecting material silicone resin solidfied material]
By making light reflecting material of the invention curability silicon-ketone composition form, solidify, light reflecting material can be obtained
With silicone resin solidfied material.Light reflecting material of the invention with curability silicon-ketone composition be applicable to injection moulding or transmitting at
The forming method that type method etc. used in the past.Further, due to light reflecting material of the invention with curability silicon-ketone composition 25
There is high fluidity at DEG C, therefore the distribution method that can not be suitable for existing solid reflector material can be utilized
(dispensing method) or perfusion (potting method) are formed.In addition, light reflecting material of the invention is used
The condition of cure of curability silicon-ketone composition is different due tos the shape of molding or curing method etc., is not particularly limited, but logical
Chang Youxuan is as follows by condition setting: at 80~200 DEG C, preferably at 100~180 DEG C, carry out 1 minute~24 hours, preferably into
Row 5 minutes~5 hours.
In general, in order to be functioned as reflector material, it is seen that the initial stage reflectivity of light (wavelength: 430~800nm)
Preferably 95% or more (that is, 95~100%), more preferably 97% or more (that is, 97~100%).If reflectivity be 95% with
On, then when solidfied material to be used as to the reflector material of the light emitting devices such as luminaire, the extraction efficiency of light becomes higher, can hold
Changing places ensures sufficient brightness.Not only the preparation initial stage of solidfied material and also heat resistant test (by 170 DEG C will solidification
Object places 1,000 hour to carry out) after, reflectivity is preferably also 82% or more, more preferably 84% or more.By light of the invention
The light reflecting material silicone resin solidfied material that reflecting material is obtained with curability silicon-ketone composition, can be made into visible light (wavelength:
430~800nm) reflectivity be 95% or more, placed 1,000 hours at 170 DEG C after light reflectivity be 82% or more
Solidfied material can obtain sufficient reflectivity as reflector material.In addition, in the present specification, the reflectivity of light refers to benefit
The numerical value measured with the spectrophotometer apparatus for being mounted with integrating sphere.
Reflector material is sliced by having used the cut off operation of scribing machine etc. sometimes.In this process, if not having
Sufficient hardness is then difficult to cut off, therefore the light reflecting material silicone resin of the invention used as reflector material solidifies
The shore D hardness of object is preferably 65 or more, and more preferably 70 or more.
[reflector and LED matrix]
Light reflecting material curability silicon-ketone composition (white Thermocurable silicon resin composition) of the invention is that light is anti-
Material use is penetrated, the purposes of the light reflecting material is not particularly limited, such as the applicable light emitting devices such as LED of making are used, particularly white
The reflector material of color LED (white light-emitting diode).It is mounted with by light reflecting material of the invention silicone resin solidfied material
The light emitting device (especially LED matrix, White LED systems etc.) of the reflector of formation can remain higher after during length
Light extraction efficiency.Further, since the mobility of composition of the invention is high, therefore is easy molding, so be easy according to containing white
These light emitting devices of color LED, the light reflecting material of the invention silicone resin solidfied material system that will be used as reflector material
At required shape.
Embodiment
Examples and Comparative Examples described below, are specifically described the present invention, but the present invention is not by following implementation
Example limitation.In addition, viscosity is spiral viscosimeter (the Malcom Co., Ltd. used as rotational viscometer in following examples
Manufacture, model: PC-1T) and measure 25 DEG C when value.
The symbol of the composition described below that silicone oil or silicone resin are indicated in following examples.In addition, each silicone oil or each silicone resin
Molal quantity indicate the molal quantity of vinyl contained in each ingredient or silicon atom bonding hydrogen atom.
MH: (CH3)2HSiO1/2
MVi: (CH2=CH) (CH3)2SiO1/2
MViΦ: (CH2=CH) (C6H5)(CH3)SiO1/2
DH: (CH3)HSiO2/2
DΦ: (C6H5)(CH3)SiO2/2
D2Φ: (C6H5)2SiO2/2
The preparation of [synthesis example 1] (A-1) ingredient
1785g (14.88 is added into the four-hole boiling flask for the 5L for having agitating device, condenser pipe, dropping funel and thermometer
Mole) vinyl norbornene (product name: V0062, Tokyo Chemical Industry Co., Ltd. manufacture；5-
The isomers of the substantially equimolar amounts of two ring of vinyl [2.2.1] hept-2-ene" and two ring of 6- vinyl [2.2.1] hept-2-ene" is mixed
Close object) and 455g toluene, using oil bath heating to 85 DEG C.The carbon dust of the platinum for being supported with 5 mass % of 3.6g is added thereto
Bis- (dimetylsilyl) benzene of Isosorbide-5-Nitrae-of 1698g (8.75 moles) were added dropwise in end through 180 minutes while stirring.After completion of dropwise addition,
24 hours heating stirrings are further carried out at 110 DEG C, are then cooled to room temperature.Then, filtering removal is supported with the carbon of platinum, subtracts
Toluene and excessive vinyl norbornene is distilled off in pressure, obtains the reaction product (25 of the colorless and transparent oily of 3362g
DEG C when viscosity: 12820mPas).
Reaction product is analyzed by FT-IR, NMR, GPC etc., the results showed that, which is following objects
The mixture of matter:
(1) have 2 compounds (example of representative configurations formula described below) to phenylene: about 41 rub
You are %；
(2) have 3 compounds (example of representative configurations formula described below) to phenylene: about 32 rub
You are %；
(3) there is 4 or more the compounds to phenylene: about 27 moles of %.
In addition, the content ratio of the addition reactivity carbon-carbon double bond of mixture entirety is 0.36 mole/100g.
[Examples 1 to 4, comparative example 1~4]
Blend following (A-1)~(H) ingredient with blended amount shown in table 1 (unit: mass parts), obtain embodiment 1~
4, each composition of comparative example 1~4.That is, firstly, with blended amount shown in table 1 to 5 liters of Frame type stirrers (INOUE MFG.,
INC. manufacture, product name: 5 liters of planetary stirring machines) in be packed into (A) ingredient, (D) ingredient, (E) ingredient and (H) ingredient, in room
Temperature lower mixing 1 hour, (B) ingredient, (F) ingredient and (G) ingredient are then added with blended amount shown in table 1, mixed at room temperature
To uniform, (C) ingredient is finally added with blended amount shown in table 1 within 30 minutes, 30 minutes is mixed under room temperature, decompression to uniform,
Obtain the curability silicon-ketone composition of white.Measure the viscosity of obtained composition.Show the result in table 1.
(A-1) reaction product obtained in synthesis example 1,
(A-2-1) Average molecular formula: MViΦ 2D2Φ 3Represented organopolysiloxane,
(A-2-2) Average molecular formula: MVi 2D2Φ 4Represented organopolysiloxane,
(A-3) Average molecular formula: MVi 2DΦ 6Represented organopolysiloxane,
(B) Average molecular formula: MH 2DH 2D2Φ 2Represented organopolysiloxane,
(C) platinum-divinyl tetramethyl disiloxane complex compound toluene solution (pt atom containing 1 mass %),
(D) titanium dioxide powder that average grain diameter is 0.5 μm,
(E) average grain diameter is the fumed silica powder of 14nm,
(F) compound represented by following formula,
(G) compound represented by following formula,
(H) 50 mass % toluene solutions (addition reaction controlling agent) of 1- acetenyl -1- cyclohexanol.
[table 1]
Then, by each composition injection mold of Examples 1 to 4, comparative example 1~4, it is made with 150 DEG C, 100Mpa
Cure under pressure 15 minutes, then solidify it 3 hours using the baking oven of 150 DEG C, normal pressure, obtains (dividing with a thickness of the solidfied material of 2mm
It Wei H1~H4, H5~H8 in table 2).The characteristic of obtained solidfied material is shown in table 2.It observes or measures in the following way
The characteristic of solidfied material.
Appearance: the surface of each solidfied material of micro- sem observation is used.According to following benchmark, table 2 is shown the result in.
Appearance uniform (zero)；Unevenness (×) caused by being agglomerated as filler
Hardness (shore D): on the basis of ASTM D 2240, the hardness (Shore D) of each solidfied material is measured.
Cutting: being coated with each composition on the copper sheet of 0.2mm thickness, makes its solidification with above-mentioned condition, prepares consolidating for 1mm thickness
Compound.After placing at room temperature, adhesive film is attached on substrate, the cutter device manufactured using DISCO Corporation
(DAD341 type), is cut to the size of 5mm × 5mm.According to following benchmark, table 2 is shown the result in.
Section is good (zero)；It generates burr (×)
Light reflectivity: the spectrophotometer apparatus U- manufactured using the Hitachi Corporation for being mounted with integrating sphere
3310, it is measured in the wavelength region of 430~800nm at 25 DEG C.
[table 2]
Then, solidfied material H1~H8 is placed 1,000 hour at 170 DEG C, carries out heat resistant test.By calculating initial stage
The light reflectivity of (before test) and the difference of the light reflectivity after test evaluate heat resistance.Show the results of the evaluation table 3.Evaluation are as follows:
The difference of light reflectivity is smaller, then heat resistance is higher.Visually to be observed, as a result all solidfied materials are white in the early stage, but
After heat resistant test, only H5 significantly changes as brown.
[table 3]
As shown in table 1~3, the light reflecting material of the invention Examples 1 to 4 of curability silicon-ketone composition is being used
In, the viscosity of composition is lower, therefore mobility is excellent.In addition, obtaining higher light reflectivity in the early stage, while resistance to
Light reflectivity also only slightly declines after heat test.I.e., it is known that heat resistance (especially resistance to thermochromism) is also excellent.
On the other hand, in comparative example 1, the light reflectivity after heat resistant test is remarkably decreased, heat resistance (especially resistance to thermal change
Color) it is poor.In comparative example 2 and 3, since the hardness of solidfied material is low, cutting is poor.In addition, being obtained not in comparative example 4
To the good appearance of solidfied material.
It is above the results show that light reflecting material curability silicon-ketone composition of the invention has high flowing at room temperature
Property, solidfied material is high rigidity, is applicable not only to cutting action, and the light reflectivity at initial stage and resistance to thermochromism are excellent.Cause
This, light reflecting material of the invention uses the solidfied material of curability silicon-ketone composition as light reflecting material, particularly as white
LED is useful with reflector material.
In addition, the present invention is not limited by above embodiment.Above embodiment is to illustrate, and is had and right of the invention
The substantially identical composition of the technical concept recorded in the claim and technical solution for playing identical function and effect is all contained in this hair
In bright technical scope.
Claims (19)
1. a kind of light reflecting material curability silicon-ketone composition, which is characterized in that contain:
(A-1) of 30~70 mass parts: (a) hydrogen in a molecule represented by the following general formula (1) with 2 with silicon atom bonding
The addition reaction product of polycycle hydrocarbon with 2 addition reactivity carbon-carbon double bonds in the compound and (b) molecule of atom,
The addition reaction product has at least two addition reactivity carbon-carbon double bond in a molecule；
(A-2) of 30~70 mass parts: compound represented by the following general formula (3), wherein (A-1) ingredient and the (A-
2) ingredient adds up to 100 mass parts；
(B) organo-silicon compound in a molecule with 3 or more with the hydrogen atom of silicon atom bonding, wherein relative to combination
Addition reactivity carbon-carbon double bond in object, in composition is with molar ratio computing with the total amount of the hydrogen atom of silicon atom bonding
0.5~3.0 amount；
(C) hydrosilylation reaction catalyst；
(D) titanium dioxide powder；And
(E) fumed silica powder,
[chemical formula 1]
In formula, A is the bivalent group in the group being made of the group represented by the following general formula (2), R1It independently is unsubstituted
Or replace carbon atom number be 1~12 monovalent hydrocarbon or carbon atom number be 1~6 alkoxy,
[chemical formula 2]
[chemical formula 3]
In formula, Ph is phenyl, R2It independently is the monovalent hydrocarbon that carbon atom number that is unsubstituted or replacing is 1~12, R3For containing adding
At the group of reactive carbon-carbon double bond, the integer that n is 1~20.
2. light reflecting material according to claim 1 curability silicon-ketone composition, which is characterized in that under (b) is
Alkenyl norbornene compound represented by general formula (4) is stated,
[chemical formula 4]
In formula, R4The alkenyl for being 2~12 for unsubstituted or substituted carbon atom number.
3. light reflecting material according to claim 1 curability silicon-ketone composition, which is characterized in that (b) is 5-
Any one in two ring of vinyl [2.2.1] hept-2-ene", two ring of 6- vinyl [2.2.1] hept-2-ene" and their combination.
4. light reflecting material according to claim 2 curability silicon-ketone composition, which is characterized in that (b) is 5-
Any one in two ring of vinyl [2.2.1] hept-2-ene", two ring of 6- vinyl [2.2.1] hept-2-ene" and their combination.
5. light reflecting material according to claim 1 curability silicon-ketone composition, which is characterized in that (B) ingredient
For silicone compounds represented by the following general formula (5),
[chemical formula 5]
In formula, R5It independently is hydrogen atom or unsubstituted in addition to alkenyl or monovalent hydrocarbon that the carbon atom number replaced is 1~12
Base, R6For methyl or hydrogen atom, the integer that p is 1~10, the integer that q is 0~7；Mark the siloxane unit of p and the silicon of mark q
Oxygen alkane unit is arranged in a manner of random mutually.
6. light reflecting material according to claim 2 curability silicon-ketone composition, which is characterized in that (B) ingredient
For silicone compounds represented by the following general formula (5),
[chemical formula 5]
In formula, R5It independently is hydrogen atom or unsubstituted in addition to alkenyl or monovalent hydrocarbon that the carbon atom number replaced is 1~12
Base, R6For methyl or hydrogen atom, the integer that p is 1~10, the integer that q is 0~7；Mark the siloxane unit of p and the silicon of mark q
Oxygen alkane unit is arranged in a manner of random mutually.
7. light reflecting material according to claim 3 curability silicon-ketone composition, which is characterized in that (B) ingredient
For silicone compounds represented by the following general formula (5),
[chemical formula 5]
In formula, R5It independently is hydrogen atom or unsubstituted in addition to alkenyl or monovalent hydrocarbon that the carbon atom number replaced is 1~12
Base, R6For methyl or hydrogen atom, the integer that p is 1~10, the integer that q is 0~7；Mark the siloxane unit of p and the silicon of mark q
Oxygen alkane unit is arranged in a manner of random mutually.
8. light reflecting material according to claim 4 curability silicon-ketone composition, which is characterized in that (B) ingredient
For silicone compounds represented by the following general formula (5),
[chemical formula 5]
In formula, R5It independently is hydrogen atom or unsubstituted in addition to alkenyl or monovalent hydrocarbon that the carbon atom number replaced is 1~12
Base, R6For methyl or hydrogen atom, the integer that p is 1~10, the integer that q is 0~7；Mark the siloxane unit of p and the silicon of mark q
Oxygen alkane unit is arranged in a manner of random mutually.
9. the curability silicon-ketone composition of light reflecting material described according to claim 1~any one of 8, which is characterized in that
Viscosity at 25 DEG C is 5~500Pa 〃 s.
10. a kind of light reflecting material silicone resin solidfied material, which is characterized in that by described in any one of claim 1~8
Curability silicon-ketone composition formed, solidified and obtained.
11. a kind of light reflecting material silicone resin solidfied material, which is characterized in that by curability silicon as claimed in claim 9
One compositions are formed, are solidified and obtained.
12. light reflecting material according to claim 10 silicone resin solidfied material, which is characterized in that after just completing solidification
The reflectivity of the light of 430~800nm of wavelength is 95% or more, the wavelength 430 under 170 DEG C of environment after exposure 1000 hours~
The reflectivity of the light of 800nm is 82% or more.
13. light reflecting material according to claim 11 silicone resin solidfied material, which is characterized in that after just completing solidification
The reflectivity of the light of 430~800nm of wavelength is 95% or more, the wavelength 430 under 170 DEG C of environment after exposure 1000 hours~
The reflectivity of the light of 800nm is 82% or more.
14. light reflecting material according to claim 10 silicone resin solidfied material, which is characterized in that shore D hardness is 65
More than.
15. light reflecting material according to claim 11 silicone resin solidfied material, which is characterized in that shore D hardness is 65
More than.
16. a kind of reflector, which is characterized in that formed by light reflecting material described in any one of claim 10 with silicone resin solidfied material.
17. a kind of reflector, which is characterized in that the light reflecting material as described in claim 11 is formed with silicone resin solidfied material.
18. a kind of LED matrix, which is characterized in that be mounted with reflector described in claim 16.
19. a kind of LED matrix, which is characterized in that be mounted with reflector described in claim 17.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018039110A JP6908546B2 (en) | 2018-03-05 | 2018-03-05 | Curable silicone composition for light reflective materials, silicone resin cured products, reflectors, and LED devices |
| JP2018-039110 | 2018-03-05 |
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| CN110229524A true CN110229524A (en) | 2019-09-13 |
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| CN201910162581.1A Active CN110229524B (en) | 2018-03-05 | 2019-03-05 | Curable silicone composition for light-reflecting material, cured silicone resin, reflector, and LED device |
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| JP (1) | JP6908546B2 (en) |
| KR (1) | KR102634630B1 (en) |
| CN (1) | CN110229524B (en) |
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| CN112625444A (en) * | 2019-10-08 | 2021-04-09 | 信越化学工业株式会社 | Addition-curable silicone composition, cured product thereof, and semiconductor device |
| CN114761489A (en) * | 2019-12-19 | 2022-07-15 | 迈图高新材料日本合同公司 | Curable composition |
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| JP7461148B2 (en) * | 2020-01-24 | 2024-04-03 | 信越化学工業株式会社 | Radical curable composition and cured product |
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Also Published As
| Publication number | Publication date |
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| KR20190105509A (en) | 2019-09-17 |
| CN110229524B (en) | 2022-03-29 |
| JP2019151768A (en) | 2019-09-12 |
| JP6908546B2 (en) | 2021-07-28 |
| KR102634630B1 (en) | 2024-02-08 |
| TW201938687A (en) | 2019-10-01 |
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