CN100366700C

CN100366700C - Curing composition and method for preparing same, light-shielding paste, light-shielding resin and method for producing same, package for light-emitting diode, and semiconductor device

Info

Publication number: CN100366700C
Application number: CNB2004800051116A
Authority: CN
Inventors: 津村学; 井手正仁; 大内克哉; 藏本雅史; 三木伦英
Original assignee: Nichia Chemical Industries Ltd; Kaneka Corp
Current assignee: Nichia Chemical Industries Ltd; Kaneka Corp
Priority date: 2003-02-25
Filing date: 2004-02-25
Publication date: 2008-02-06
Anticipated expiration: 2024-02-25
Also published as: CN1753966A; CN101197408B; CN101197408A

Abstract

A light-shielding paste composed of a specific component and an inorganic material is disclosed. A method for providing an LED package with a light-shielding resin layer by applying the light-shielding paste only to the side walls of the package is also disclosed. Since the light-shielding paste has a low fluidity, it is possible to form a cured product thereof only on the side walls of the LED package. With this light-shielding resin layer forming method, light-shielding resin layers can be efficiently formed only on the side walls of the LED packages, thereby greatly improving the productivity.

Description

Solidification compound and modulator approach thereof, light-shielding paste, light-shielding resin and forming method thereof, the effective shell of light-emitting diodes and semiconductor device

Technical field

The effective shell of light-emitting diodes that the present invention relates to the formation method of the modulator approach, light-shielding paste of solidification compound, solidification compound, light-shielding resin that the curing light-shielding paste obtains, light-shielding resin, coats with light-shielding resin and as the photodiode of semiconductor device.In more detail, relate to solidification compound excellent in adhesion, as to have high opacifying property, even more ideal be low curtain coating and solidification compound with suitable operability.In addition, only relate at LED and form the method for light-shielding resin layer efficiently, only form the photodiode of light shield layer with the peristome sidewall of shell at LED with the peristome sidewall of shell.

Background technology

In recent years, photodiode (below be also referred to as LED) utilize the expansion in field the time, seeking reliability higher, can be for a long time and the photodiode of high brightness luminescent.Photodiode by outer electrode, led chip, will constitute from shell and the mould sealing that the light of led chip is derived the peristome of the bottom surface of usefulness and sidewall efficiently.Form outer electrode at shell underrun monolithic molding, conduct to the outside well, form the high noble metal film of luminous reflectance factor in order to make light.On the other hand, because shell generally is an organic resin, therefore, during its sidewall of light prolonged exposure, can produce because the deterioration of shell resin cementability that cause and the mould sealing reduces, and because the reflectivity that the shell coloring resin causes reduces degradation problem under the brightness of LED.

Therefore, be not purpose directly with LED with shell, and/or can be reduced to purpose, seek to protect the light-shielding paste of shell resin owing to the painted reflectivity that causes of shell resin by irradiate light.

In the past, in add-on type reaction-curable (hydrosilylation) polysiloxane, contain that epoxy group(ing) and alkoxyl group are combined in silicoorganic compound on the Siliciumatom and the solidification compound of organo-aluminium compound shows good adaptation, proposed to be applied to the technology (spy opens flat 08-183934 communique, the spy opens flat 05-140459 communique) of adhesive sheet, processing cloth etc.But from the viewpoint of optical characteristics, the material that these technology obtain is inappropriate as the effective light-shielding resin of light-emitting diodes.In addition, proposed in add-on type reaction-curable (hydrosilylation) liquid composition, to add Resins, epoxy and aluminum compound, improved the technology (No. the 3354973rd, patent) of cementability.But, about the effective light-shielding resin of light-emitting diodes without any open.

In addition, proposition is in condensation reaction curing polysiloxane, when using as the sealing material of buildings seam portion, by adding boric acid ester, even under the very shallow situation of joint depth, also can show good cementability (spy opens clear 59-155483 communique) with adherend.But this system is self-vulcanizing, and effect that shows when being heating and curing or the effect that shows when being used in the different addition reaction-type system of reaction formation are without any open.

On the other hand, knownly contain two in 1 molecule at least and have the cured article that the solidification compound of the compound that contains two SiH bases in the organic compound of reactive carbon-to-carbon double bond, the molecule at least, hydrosilylation catalysts constitutes, can be used as the effective sealing agent of light-emitting diodes and use (spy opens the 2002-314140 communique) with the SiH base by comprising.But, for as the cementability after the rayed of the effective light-shielding resin necessity of light-emitting diodes without any open.

, though this light shield layer can make solidification compound be solidified to form,, if the curtain coating height of solidification compound, can curtain coating during curing to shell bottom surface curtain coating, have the problem of the light shield layer that can not get expecting thickness.In addition, if the curtain coating height of solidification compound can produce and pollute the bottom surface, for example can not obtain problem to the conducting of the blaster fuse frame material that is arranged on the bottom surface.

Have, existence does not also have to obtain can be only in the problem of LED with the effective ways of the sidewall coating of shell peristome again.In addition, the present invention said " only LED with the coating of the sidewall of shell peristome " though the meaning be that light-shielding paste of the present invention flows out near the bottom surface the sidewall and when solidifying, only otherwise brought baneful influence, just comprise this situation as the performance of final photodiode.

Summary of the invention

Brief summary of the invention

Therefore, first purpose of the present invention provides excellent in adhesion and has the solidification compound of high opacifying property, also provides mobile low solidification compound, the modulator approach of this solidification compound, the light-shielding paste that comprises this solidification compound, cured article, curing light-shielding paste and the light-shielding resin that obtains and in fact only carry out shading with the sidewall of shell by light-shielding paste and/or light-shielding resin and the photodiode that forms at LED.

In addition, second purpose of the present invention only provide LED with the sidewall of shell peristome form efficiently the light-shielding resin layer method, be fit to the light-shielding paste of this method, the light-shielding resin that forms by this method, with the LED of this light-shielding resin coating sidewall with shell, only form the photodiode that light shield layer obtains with shell peristome sidewall at LED by this method.

For solving found that related problem present inventors further investigate, by

Contain thermoplastic resin and inorganic materials light-shielding paste as neccessary composition; Contain heat-curing resin and inorganic materials light-shielding paste as neccessary composition; Comprise contain at least in (A) 1 molecule 2 with the SiH base have the compound that contains silicon compound, (C) hydrosilylation catalysts, (D) silane coupling agent of 2 SiH bases at least in molecule of organic compound, (B) that the organic class skeleton of reactive carbon-to-carbon double bond constitutes and/or contain epoxy group(ing), (E) silanol condensation catalyst and (F) inorganic materials as the solidification compound of neccessary composition; The above-mentioned solidification compound that also contains (G) silicon-dioxide; On the glass basis material that the angles of 80 degree tilt, under 100 ℃, through the curtain coating after 1 hour at 2cm or the above-mentioned solidification compound below the 2cm; The light-shielding paste that comprises above-mentioned solidification compound; Perhaps has the peristome that constitutes by bottom surface and sidewall, and, the LED shell that each end of positive outer electrode and negative outer electrode obtains with the shaping resin monolithic molding according to the interval that is separated out regulation with exposing in the peristome bottom surface, in this shell, (1) on the light-shielding paste that is coated on the body material, (2) driving fit LED is with behind the peristome of shell, (3) by LED is heated with the state that makes progress with the peristome of shell, with light-shielding paste only in the formation method of the light-shielding resin layer of the sidewall curtain coating of shell, solve above-mentioned problem, so far finished the present invention.

That is, first of the present invention is,

A kind of light-shielding paste (1 of claim the) is characterized in that, comprises thermoplastic resin and inorganic materials as neccessary composition,

A kind of light-shielding paste (2 of claims the) is characterized in that, comprises thermosetting resin and inorganic materials as neccessary composition,

Claim 1 or 2 light-shielding pastes of being put down in writing (3 of claims the) is characterized in that inorganic materials is a titanium oxide,

A kind of light-shielding paste (4 of claims the) is characterized in that the titanium oxide of being put down in writing in the claim 3 is a rutile-type, and its median size is 0.1～1.0 μ m,

A kind of solidification compound (5 of claims the), it is characterized in that, said composition contain (A) comprise contain at least in 1 molecule 2 with the SiH base have the compound that contains silicon compound, (C) hydrosilylation catalysts, (D) silane coupling agent of 2 SiH bases at least in molecule of organic compound, (B) of organic class skeleton of reactive carbon-to-carbon double bond and/or contain epoxy group(ing), (E) silanol condensation catalyst and (F) inorganic materials as neccessary composition

The solidification compound that claim 5 is put down in writing (6 of claims the) is characterized in that (F) composition is a titanium oxide,

The solidification compound that claim 6 is put down in writing (7 of claims the) is characterized in that titanium oxide is a rutile-type, and its median size is 0.1～1.0 μ m,

Any solidification compound of being put down in writing (8 of claims the) in the claim 5～7; it is characterized in that; (D) composition is to have at least 1 functional group selecting from the group that comprises epoxy group(ing), methacryloyl, acryl, isocyanate group, tricarbimide ester group, vinyl and carbamate groups and the silane coupling agent of water-disintegrable silicon group in the molecule

Any solidification compound of being put down in writing (9 of claims the) is characterized in that in the claim 5～8, and (D) composition is the silane coupling agent that has epoxy group(ing) and water-disintegrable silicon group in the molecule,

Any solidification compound of being put down in writing (10 of claims the) is characterized in that in the claim 5～9, and (E) composition is select from organo-aluminium compound and boric acid ester at least a,

Any solidification compound of being put down in writing (11 of claims the) is characterized in that in the claim 5～10, and (E) composition is at least a kind that selects from aluminium chelate compound and aluminium-alcohol salt compound,

Any solidification compound of being put down in writing (12 of claims the) in the claim 5～10, it is characterized in that, (E) composition is to close aluminium, ethyl-diacetyl-acetate single acetyl acetone and close aluminium, tri acetylacetonato and close at least a kind that selects the group of aluminium from comprising methyl aceto acetate aluminum-diisopropoxide, methyl aceto acetate two isobutanol aluminums, three (methyl aceto acetates)

Any solidification compound of being put down in writing (13 of claims the) in the claim 5～10, it is characterized in that, (E) composition is at least a kind that selects from the group that comprises boric acid three Octadecane base esters, boric acid three n-octyls, tri-n-butyl borate, triisopropyl borate ester, boric acid three n-propyls, triethyl borate and trimethyl borate

Any solidification compound of being put down in writing (14 of claims the) is characterized in that in the claim 5～13, and (A) composition contains useful following general formula (I)

(in the formula, R ¹Any monovalent organic radical group of expression carbonatoms 1～50, each R ¹Can difference also can be identical) organic compound of expression,

Any solidification compound of being put down in writing (15 of claims the) is characterized in that (A) composition is a triallyl isocyanurate in the claim 5～14, (B) composition is 1,3,5, the reaction product of 7-tetramethyl-ring tetrasiloxane and triallyl isocyanurate

Any solidification compound of being put down in writing (16 of claims the) in the claim 5～14, it is characterized in that, (A) composition is the mixture of triallyl isocyanurate and single glycidyl diallyl chlorinated isocyanurates, (B) composition is 1,3,5, the reaction product of 7-tetramethyl-ring tetrasiloxane and triallyl isocyanurate

Any solidification compound of being put down in writing (17 of claims the) is characterized in that in the claim 5～16, also contains (G) silicon-dioxide,

The solidification compound that claim 17 is put down in writing (18 of claims the) is characterized in that, on the glass basis material that the angles of 80 degree tilt, under 100 ℃, through the curtain coating of the solidification compound after 1 hour at 2cm or below the 2cm,

Claim 17 or 18 solidification compounds of being put down in writing (19 of claims the) is characterized in that, said composition is in having mixed the mixture of ingredients of (A) composition～(E), mix (F) composition and (G) composition and making,

Any solidification compound of being put down in writing (20 of claims the) is characterized in that in the claim 17～19, and (G) median size of the primary particle of silicon-dioxide is 3～20nm,

The method (21 of claims the) of any solidification compound of being put down in writing in the preparation claim 17～20, it is characterized in that, in having mixed (A)～(E) mixture of ingredients, use planetary stirring deaeration machine, mix (F) composition and (G) composition

The method (22 of claims the) of any solidification compound of being put down in writing in the preparation claim 17～20 is characterized in that, in having mixed (A)～(E) mixture of ingredients, uses dissolver, mixes (F) composition and (G) composition,

A kind of light-shielding paste (23 of claims the) is characterized in that, this paste comprises any solidification compound of being put down in writing in the claim 5～20,

A kind of cured article (24 of claims the) is characterized in that, any solidification compound of being put down in writing obtains in this cured article curing claim 5～20,

A kind of light-shielding resin (25 of claims the) is characterized in that, any light-shielding paste of being put down in writing obtains in this resin curing claim 1～4,23,

A kind of LED is characterized in that in fact only having 25 light-shielding resins of being put down in writing of claim the on the sidewall of LED with the shell peristome with shell (26 of claims the),

The LED that claim 26 is put down in writing is characterized in that with shell (27 of claims the) the LED shell is a resin manufacture,

The LED that claim 26 is put down in writing is characterized in that with shell (28 of claims the) LED is the composition that contains the fluoropolymer resin of hemicrystalline with the shaping resin of shell,

The LED that claim 26 is put down in writing is characterized in that with shell (29 of claims the) the LED shell is a pottery manufacturing,

The LED that claim 26 is put down in writing is characterized in that with shell (30 of claims the) LED is a rectangle with the peristome of shell,

The LED that claim 26 is put down in writing is characterized in that with shell (31 of claims the) LED is circular with the peristome of shell,

The LED that claim 26 is put down in writing is characterized in that with shell (32 of claims the) LED is oval with the peristome of shell,

A kind of semiconductor device (33 of claims the), this device is to have to possess the peristome that comprises bottom surface and sidewall, and in the peristome bottom surface, each end of positive outer electrode and the outer electrode of bearing, the LED shell that obtains with the shaping resin monolithic molding according to the interval of separating regulation with exposing, semiconductor device with the luminous element that on the bottom surface of LED, is provided with shell, it is characterized in that, in fact only this LED with the sidewall of shell on the coating claim 5～20 in any solidification compound of being put down in writing, and/or form the cured article that claim 24 is put down in writing

A kind of semiconductor device (34 of claims the), this device is to have to possess the peristome that comprises bottom surface and sidewall, and in the peristome bottom surface, each end of positive outer electrode and the outer electrode of bearing, the LED shell that obtains with the shaping resin monolithic molding according to the interval of separating regulation with exposing, semiconductor device with the luminous element that on the bottom surface of LED, is provided with shell, it is characterized in that, in fact only in this LED coating claim 1～4 on the sidewall of shell, any light-shielding paste of being put down in writing and/or form light-shielding resin that claim 25 puts down in writing and shading in 23

Claim 33 or 34 semiconductor devices of being put down in writing (35 of claims the) is characterized in that the shaping resin of shell is the composition that contains the fluoropolymer resin of hemicrystalline.

In addition, second of the present invention is,

The formation method of light-shielding resin layer (36 of claims the), it is characterized in that, has the peristome that comprises bottom surface and sidewall and each end of positive outer electrode and negative outer electrode in the peristome bottom surface, the LED that obtains with the shaping resin monolithic molding according to the interval of separating regulation with in the shell with exposing

(1) on the light-shielding paste of coating on the body material,

(2) after driving fit LED uses the peristome of shell,

(3) LED is heated with the state that makes progress with the peristome of shell,

Thus, with light-shielding paste curtain coating on the sidewall of shell only,

The formation method of the light-shielding resin layer that claim 36 is put down in writing (37 of claims the) is characterized in that, light-shielding paste is coated on the plane body material of selecting from flat board, leveling board, tabular band, Δ shape cylinder group,

The formation method of the light-shielding resin layer that claim 36 is put down in writing (38 of claims the) is characterized in that, light-shielding paste is coated on the curved surface shape body material of selecting from the group that cylinder, ball constitute,

The formation method of the light-shielding resin layer that claim 36 is put down in writing (39 of claims the) is characterized in that in the operation that LED is heated with the state that makes progress with the shell peristome (3), heat the piecewise,

The formation method of the light-shielding resin layer that claim 36 is put down in writing (40 of claims the) is characterized in that LED is a rectangle with the peristome of shell, and bond length is 100 μ m or more than the 100 μ m,

The formation method of the light-shielding resin layer that claim 36 is put down in writing (41 of claims the) is characterized in that, LED is circular with the peristome of shell,

The formation method of the light-shielding resin layer that claim 36 is put down in writing (42 of claims the) is characterized in that, LED is oval with the peristome of shell,

The formation method of any light-shielding resin layer of being put down in writing in the claim 36～42 (43 of claims the) is characterized in that, the viscosity of light-shielding paste is being more than 10 pools or 10 are moored under the normal temperature (23 ℃), and (30 ℃) are more than 1 pool or 1 is moored during heating,

The formation method of any light-shielding resin layer of being put down in writing in the claim 36～42 (44 of claims the) is characterized in that, light-shielding paste is 0.8～1.2 23 ℃ thixotropy (viscosity ratio),

The formation method of any light-shielding resin layer of being put down in writing in the claim 36～42 (45 of claims the), it is characterized in that, is 15 seconds～90 seconds with light-shielding paste in the set time that time (ス Na Star プア Star プィ system) mensuration is regulated in 115 ℃ locking key

The formation method of any light-shielding resin layer of being put down in writing in the claim 36～42 (46 of claims the), it is characterized in that, after being coated on the sheet glass with the round shape of 8mm diameter the 50mg light-shielding paste, this sheet glass is fixed with tilting 80 degree, 21 ℃ of distances that time flowed down that kept 10 minutes down is 5mm～30mm

The formation method of any light-shielding resin layer of being put down in writing in the claim 36～42 (47 of claims the), it is characterized in that, after being coated on the sheet glass with the round shape of 8mm diameter the 50mg light-shielding paste, this sheet glass is fixed with tilting 80 degree, the distance that time flowed down that kept 5 minutes in the time of 60 ℃ is 10mm～70mm

The formation method of any light-shielding resin layer of being put down in writing in the claim 36～42 (48 of claims the) is characterized in that, light-shielding paste contains thermoplastic resin and inorganic materials as neccessary composition,

The formation method of any light-shielding resin layer of being put down in writing in the claim 36～42 (49 of claims the) is characterized in that, light-shielding paste contains thermosetting resin and inorganic materials as neccessary composition,

The formation method of any light-shielding resin layer of being put down in writing in the claim 36～42 (50 of claims the) is characterized in that light-shielding paste is by containing

(A) contain at least in 1 molecule 2 with the SiH base have the compound that contains silicon compound, (C) hydrosilylation catalysts, (D) silane coupling agent of 2 SiH bases at least in molecule of organic compound, (B) of organic class skeleton of reactive carbon-to-carbon double bond and/or contain epoxy group(ing), (E) silanol condensation catalyst and (F) inorganic materials be the light-shielding paste that the solidification compound of feature forms as neccessary composition

The formation method of any light-shielding resin layer of being put down in writing in the claim 48～50 (51 of claims the) is characterized in that inorganic materials is a titanium oxide,

The formation method of the light-shielding resin layer that claim 51 is put down in writing (52 of claims the) is characterized in that titanium oxide is a rutile-type, and its median size is 0.1～1.0 μ m,

The formation method of any light-shielding resin layer of being put down in writing in the claim 48～50 (53 of claims the) is characterized in that, also contains (G) silicon-dioxide,

The formation method of the light-shielding resin layer that claim 53 is put down in writing (54 of claims the) is characterized in that silicon-dioxide is hydrophobic silica,

The formation method of the light-shielding resin layer that claim 50 is put down in writing (55 of claims the); it is characterized in that; (D) composition is to have at least 1 functional group selecting from the group of epoxy group(ing), methacryloyl, acryl, isocyanate group, tricarbimide ester group, vinyl and carbamate groups and the silane coupling agent of water-disintegrable silicon group in the molecule

The formation method of the light-shielding resin layer that claim 50 is put down in writing (56 of claims the) is characterized in that (D) composition is the silane coupling agent that has epoxy group(ing) and water-disintegrable silicon group in the molecule,

The formation method of the light-shielding resin layer that claim 50 is put down in writing (57 of claims the) is characterized in that (E) composition is select at least a from organo-aluminium compound and boric acid ester,

The formation method of the light-shielding resin layer that claim 50 is put down in writing (58 of claims the) is characterized in that (E) composition is at least a kind that selects from aluminium chelate compound and aluminium-alcohol salt compound,

The formation method of the light-shielding resin layer that claim 50 is put down in writing (59 of claims the), it is characterized in that, (E) composition is to close aluminium, ethyl-diacetyl-acetate single acetyl acetone and close aluminium, tri acetylacetonato and close at least a kind that selects the group of aluminium from comprising methyl aceto acetate aluminum-diisopropoxide, methyl aceto acetate two isobutanol aluminums, three (methyl aceto acetates)

The formation method of the light-shielding resin layer that claim 50 is put down in writing (60 of claims the), it is characterized in that, (E) composition is at least a kind that selects from the group that comprises boric acid three Octadecane base esters, boric acid three n-octyls, tri-n-butyl borate, triisopropyl borate ester, boric acid three n-propyls, triethyl borate and trimethyl borate

The formation method of the light-shielding resin layer that claim 50 is put down in writing (61 of claims the) is characterized in that (A) composition contains useful following general formula (I)

The formation method of the light-shielding resin layer that claim 50 is put down in writing (62 of claims the) is characterized in that (A) composition is a triallyl isocyanurate, and (B) composition is 1,3,5, the reaction product of 7-tetramethyl-ring tetrasiloxane and triallyl isocyanurate,

The formation method of the light-shielding resin layer that claim 50 is put down in writing (63 of claims the), it is characterized in that, (A) composition is the mixture of triallyl isocyanurate and single glycidyl diallyl chlorinated isocyanurates, (B) composition is 1,3,5, the reaction product of 7-tetramethyl-ring tetrasiloxane and triallyl isocyanurate

A kind of light-shielding resin (64 of claims the), it is characterized in that, yellow chromaticity (the yellowness index of the light-shielding resin that the formation method by any light-shielding resin layer of being put down in writing in the claim 36～42 forms, YI), with its initial value as 100 o'clock, in the value of heating after 3 minutes under 260 ℃ is 100～150

A kind of light-shielding resin (65 of claims the), it is characterized in that, yellow chromaticity (the yellowness index of the light-shielding resin that the formation method by any light-shielding resin layer of being put down in writing in the claim 36～42 forms, YI), with its initial value as 100 o'clock, the value that use xenon weathering test instrument carries out behind the light fastness test is 100～150

A kind of light-shielding resin (66 of claims the) is characterized in that, the thickness of the light-shielding resin that the formation method by any light-shielding resin layer of being put down in writing in the claim 36～42 forms is 1～1000 μ m,

A kind of light-shielding resin (67 of claims the), it is characterized in that, the light-shielding resin that formation method by any light-shielding resin layer of being put down in writing in the claim 36～42 forms and the bonding strength of substrate, with its initial value as 100 o'clock, the value that use xenon weathering test instrument carries out behind the light fastness test is more than 70 or 70

A kind of LED is characterized in that with shell (68 of claims the) the formation method coating light-shielding paste by any light-shielding resin layer of being put down in writing in the claim 36～63 forms the light-shielding resin layer,

The LED that claim 68 is put down in writing is characterized in that with shell (69 of claims the) the LED shell is a resin manufacture,

The LED that claim 68 is put down in writing is characterized in that with shell (70 of claims the) LED contains the semicrystalline polymeric resin with shell,

The LED that claim 68 is put down in writing is characterized in that with shell (71 of claims the) the LED shell is a pottery manufacturing,

A kind of semiconductor device (72 of claims the), this device is to have to possess the peristome that comprises bottom surface and sidewall, and in the peristome bottom surface, each end of positive outer electrode and the outer electrode of bearing, the LED shell that obtains with the shaping resin monolithic molding according to the interval of separating regulation with exposing, semiconductor device with the luminous element that on the bottom surface of LED, is provided with shell, it is characterized in that, in fact only at the sidewall of this LED with shell, formation method by any light-shielding resin layer of being put down in writing in the claim 36～63, form light-shielding resin and shading

The semiconductor device that claim 72 is put down in writing (73 of claims the) is characterized in that the LED shell is a resin manufacture,

The semiconductor device that claim 72 is put down in writing (74 of claims the) is characterized in that LED contains the semicrystalline polymeric resin with shell,

The semiconductor device that claim 72 is put down in writing (75 of claims the) is characterized in that, the LED shell is a pottery manufacturing,

A kind of semiconductor device (76 of claims the), this device is to have to possess the peristome that comprises bottom surface and sidewall and in the peristome bottom surface, each end of positive outer electrode and the outer electrode of bearing, the LED shell that obtains with the shaping resin monolithic molding according to the interval of separating regulation with exposing, semiconductor device with the luminous element that on the bottom surface of LED, is provided with shell, it is characterized in that, form light-shielding resin and shading on the bottom surface of shell and sidewall at the LED around the luminous element.

The detailed content of invention

Below, describe the present invention in detail.

＜first of the present invention

Said light-shielding paste contains resin and inorganic materials as neccessary composition among the present invention, optionally, can contain other additive such as viscosity modifier, cementability imparting agent, solvent.In addition, this light-shielding paste is coated by on the adhesion, protected this not influenced by light by adhesion.

Light-shielding paste of the present invention can be enumerated, and contains thermoplastic resin and inorganic materials and be neccessary composition, and to contain heat-curing resin and inorganic materials be neccessary composition.

Can use various resins as the thermoplastic resin that is used among the present invention.For example, can give an example out, butyl polyacrylate resinoids such as monomeric random, block of the homopolymer of polymethylmethacrylate resinoids (for example Hitachi changes into the system ォプトレッ of society Star etc.) such as monomeric random, block of the homopolymer of methyl methacrylate and methyl methacrylate and other or graftomer, butyl acrylate and butyl acrylate and other or graftomer etc. are the acrylic resin of representative; Contain with dihydroxyphenyl propane, 3,3,5-trimethylammonium cyclohexylidene bis-phenol etc. are as the polycarbonate resins such as polycarbonate resin (for example Supreme Being people society makes APEC etc.) of monomer structure; The resin that homopolymerization such as norbornene derivative, vinyl monomer or copolymerization obtain, norbornene derivative is carried out the resin that ring-opening metathesis polymerization obtains, or the cycloolefin resinoid of its hydride etc. (for example, Mitsui Chemicals society system APEL, Japanese ゼォ Application society system ZEONOR, ZEONEX, the system ARTON of JSR society etc.); Alkene-maleimide resins such as the multipolymer of ethene and maleimide (for example eastern ソ system TI-PAS of one society etc.); Glycolss such as bisphenols such as dihydroxyphenyl propane, two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes and glycol ether, the polyester resins such as polyester (for example bell spins the system O-PET of society etc.) that form with phthalic acid class such as terephthalic acid, m-phthalic acid or the polycondensation of aliphatic dicarboxylic acid class; Polyethersulfone resin; Polyarylate resin; Polyvinyl acetal resin; Polyvinyl resin; Acrylic resin; Polystyrene resin; Polyamide resin; Silicone resin; Beyond the fluoro-resin etc., also have rubber-like resins such as natural rubber, EPDM etc., still, be not limited to these.

From with the cementability viewpoint of LED with the sidewall of shell, preferred acrylic resin, polyamide resin, polyester resin.In addition, from sunproof viewpoint, preferred silicone resin, fluoro-resin etc.

Also can have crosslinkable groups as thermoplastic resin, for example can contain in the molecule with SiH and have reactive carbon-to-carbon double bond and/or contain the SiH group.On the crosslinked body that obtains becomes stronger and more unyielding this point easily, contain in the preferred molecule to have and on average contain the SiH group in reactive carbon-to-carbon double bond and/or 1 molecule more than 1 or 1 with the SiH group.As other crosslinkable groups, can enumerate epoxy group(ing), amido, free-radical polymerised unsaturated group, carboxyl, isocyanate group, hydroxyl, alkoxysilyl etc.On the viewpoint that the thermotolerance of the crosslinked body that obtains becomes higher easily, on average contain the bridging property base in preferred 1 molecule more than 1 or 1.

As the molecular weight of thermoplastic resin, there is no particular limitation, but on the coating this point, and preferred number average molecular weight is more preferably below 5000 or 5000 below 10000 or 10000.Also there is no particular limitation about the distribution of molecular weight, but reduce in the viscosity of mixture, coating becomes on the better this point easily, preferred molecular weight is distributed as below 3 or 3, below more preferred 2 or 2, below preferred especially 1.5 or 1.5.In addition, number-average molecular weight can be measured by gel permeation chromatography.

Can use singlely as thermoplastic resin, also can a plurality ofly be used in combination.

Use level as the thermoplastic resin in the light-shielding paste has no particular limits, and preferred usage quantity is 0.1～90 weight % of light-shielding paste total amount of the present invention.From the good viewpoint of coating, the scope of preferred usage quantity is 10 weight % of light-shielding paste total amount or 10 weight % are above, comparative optimization 40 weight % or 40 weight % are above, more preferred 60 weight % or 60 weight % are above, preferred especially 80 weight % or more than the 80 weight %.If use level is few, then coating reduces, because coating is bad, and the tendency that exists opacifying property to reduce easily.In addition, from the good viewpoint of shading, the scope of preferred usage quantity is 90 weight % of light-shielding paste total amount or 90 weight % are following, comparative optimization 80 weight % or 80 weight % are following, more preferred 60 weight % or 60 weight % are following, preferred especially 50 weight % or 50 weight % are following, very preferred 30 weight % or below the 30 weight %.If the use level of thermoplastic resin is many, there is the tendency that the inorganic materials of adding tails off, opacifying property reduces easily.Therefore, for having both coating and opacifying property, 10 weight %～80 weight %, the comparative optimization 10 weight %～50 weight % that preferred usage quantity scope is whole light-shielding paste total amounts, be more preferably 10 weight %～30 weight %.

Thermoplastic resin can directly mix with the inorganic materials of following middle explanation, also can also adopt uniform dispersion state and/or the admixture of removing solvent afterwards with uniform mixing such as solvents.When disperseing to use thermoplastic resin, all settings can be done in its averaged particles footpath, and the lower limit of preferred median size is 10nm, and the upper limit of preferred median size is 10 μ m.The distribution of particle system also can be arranged, and can be single dispersion, also can have a plurality of peak value particle diameters, the better viewpoint but, coating low from the viscosity of light-shielding paste becomes easily, and the coefficient of variation of preferable particle size is below 10% or 10%.

As the heat-curing resin that is used in light-shielding paste of the present invention, can use various kinds of resin.As heat-curing resin, can give an example out, Resins, epoxy, isocyanate resin, resol, polyimide resin, urethane resin, bimaleimide resin etc., but be not limited to these.Wherein, from the viewpoint of practical excellents such as cementability, preferred epoxy.

As Resins, epoxy, can enumerate, for example, with phenolic varnish phenol type Resins, epoxy, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin, the Bisphenol F diglycidylether, bisphenol A diglycidyl ether, 2,2 '-two (4-glycidoxypropyl cyclohexyl) propane, 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, the vinyl cyclohexene dioxide, 2-(3, the 4-epoxycyclohexyl)-5,5-spiral shell-(3, the 4-epoxy cyclohexane)-1, the 3-diox, two (3, the 4-epoxycyclohexyl)-adipic acid ester, 1,2-cyclopropane dicarboxylic acid bisglycidyl ester, isocyanuric acid three-glycidyl ester, monoene propyl group Diglycidylisocyanury-ester, Resins, epoxy such as single glycidyl diallyl chlorinated isocyanurates are used hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, the trialkyl Tetra Hydro Phthalic Anhydride, aliphatic anhydride such as carbic anhydride are solidified the material that obtains.These Resins, epoxy or solidifying agent can use separately also respectively and can a plurality ofly be used in combination.

Heat-curing resin can use separately, also can a plurality ofly be used in combination.

Use level as the heat-curing resin in the light-shielding paste has no particular limits, and preferred usage quantity is 0.1～90 weight % of light-shielding paste total amount of the present invention.From the good viewpoint of coating, the scope of preferred usage quantity is 10 weight % of light-shielding paste total amount or 10 weight % are above, comparative optimization 40 weight % or 40 weight % are above, more preferred 60 weight % or 60 weight % are above, preferred especially 80 weight % or more than the 80 weight %.If use level is few, then coating reduces, because coating is bad, and the tendency that exists opacifying property to be easy to reduce.In addition, from the good viewpoint of opacifying property, the scope of preferred usage quantity is 90 weight % of light-shielding paste total amount or 90 weight % are following, comparative optimization 80 weight % or 80 weight % are following, more preferred 60 weight % or 60 weight % are following, preferred especially 50 weight % or 50 weight % are following, very preferred 30 weight % or below the 30 weight %.If the use level of thermosetting resin is many, there is the tendency that inorganic materials tails off and opacifying property is easy to reduce that makes interpolation.Therefore, for having both coating and opacifying property, 10 weight %～80 weight %, the comparative optimization 10 weight %～50 weight % that preferred usage quantity scope is the light-shielding paste total amount, be more preferably 10 weight %～30 weight %.

Thermosetting resin can directly mix with the inorganic materials of following middle explanation, also can adopt uniform dispersion state and/or the admixture of removing solvent also passable afterwards with uniform mixing such as solvents.When disperseing to use thermosetting resin, its median size can be done all settings, but the lower limit of preferred median size is 10nm, and the upper limit of preferred median size is 10 μ m.The distribution of particle system also can be arranged, and can be single dispersion, also can have a plurality of peak value particle diameters, the better viewpoint but, formability low from the viscosity of light-shielding paste becomes easily, and the coefficient of variation of preferable particle size is below 10% or 10%.

In the thermosetting resin in being used in light-shielding paste, from the stable on heating viewpoint of photostabilization, the thermosetting resin of explanation in 5 of the preferred claims the.

Be used in inorganic materials expectation of the present invention and be dispersed in the resin, and can reflect the light next from the outside.As such inorganic materials, can enumerate, for example oxide compounds such as aluminum oxide, titanium oxide, stannic oxide, zinc oxide, tin protoxide, calcium oxide, magnesium oxide, beryllium oxide; Metal nitrides such as boron nitride, silicon nitride, aluminium nitride; Metallic carbide such as SiC; Metal carbonates such as lime carbonate, salt of wormwood, yellow soda ash, magnesiumcarbonate, barium carbonate; Metal hydroxides such as aluminium hydroxide, magnesium hydroxide; Aluminum borate, barium titanate, Calucium Silicate powder, clay, gypsum, barium sulfate, mica, diatomite, carclazyte, inorganic hollow ball material (balloon), fluorescent substance etc.These can use separately, also can more than 2 kinds or 2 kinds and use.

Inorganic materials can be carried out suitable surface treatment.As surface treatment, can enumerate by alkylation processing, trimethyl silyl processing, polysiloxane handle, coupler is handled etc.

As the example of coupler at this moment, can enumerate silane coupling agent.As silane coupling agent, to have a compound of reactive functional group and water-disintegrable silicon group just passable so long as have at least one and organic group in the molecule respectively, and there is no particular limitation.

As having reactive functional group with organic group; viewpoint from operability; preferred at least one functional group of from epoxy group(ing), methacryloyl, acryl, isocyanate group, tricarbimide ester group, vinyl, carbamate groups, selecting; from the viewpoint of solidified nature and cementability, preferred especially epoxy group(ing), methacryloyl, acryl.As water-disintegrable silicon group, from the viewpoint of operability, preferred alkoxysilyl, from reactive this viewpoint, preferred especially methoxy methyl silylation, (ethoxymethyl) silylation.

As preferred silane coupling agent, can give an example out, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane etc. have the alkoxyl silicone alkanes of epoxy-functional; 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, 3-acryloxy propyl trimethoxy silicane, 3-acryloxy propyl-triethoxysilicane, methacryloxy methyltrimethoxy silane, methacryloxy Union carbide A-162, acryloxy methyltrimethoxy silane, acryloxy Union carbide A-162 etc. have the alkoxyl silicone alkanes of methacryloyl or acryl.

As the use level of the inorganic materials in the light-shielding paste, there is no particular limitation, and preferred usage quantity is 0.1～90 weight % of light-shielding paste total amount of the present invention.From the good viewpoint of coating, preferred usage quantity is 80 weight % of light-shielding paste total amount or 80 weight % are following, comparative optimization 70 weight % or 70 weight % are following, more preferred 50 weight % or 50 weight % are following, preferred especially 40 weight % or below the 40 weight %, preferred more especially 30 weight % or below the 30 weight %.If use level is many, then coating reduces, owing to the bad tendency that makes opacifying property be easy to reduce that exists of coating.In addition, from the good viewpoint of opacifying property, preferred usage quantity is 5 weight % of light-shielding paste total amount or 5 weight % are above, comparative optimization 10 weight % or 10 weight % are above, more preferred 30 weight % or 30 weight % are above, preferred especially 40 weight % or 40 weight % are above, very preferred 50 weight % or more than the 50 weight %.Therefore, for having both coating and opacifying property, 10 weight %～80 weight %, the comparative optimization 20 weight %～70 weight % that preferred usage quantity is the light-shielding paste total amount, be more preferably 30 weight %～60 weight %.

The shape of inorganic materials when considering dispersiveness or opacifying property, can be made different shapes such as glomeration, needle-like, flakey.

In addition, the median size of inorganic materials is that the various particles of 1nm～100 μ m all are fit to use, but from the viewpoint to the dispersiveness of resin, preferred 1.0 μ m or below the 1.0 μ m, comparative optimization 0.8 μ m or below the 0.8 μ m is more preferably 0.4 μ m or below the 0.4 μ m.In addition, from the viewpoint of the power of covering, preferred 0.1 μ m or more than the 0.1 μ m is more preferably 0.2 μ m or more than the 0.2 μ m.Therefore from having both dispersiveness and the viewpoint of covering power, the preferred 0.1 μ m of median size～1.0 μ m.In addition, this median size can be that survey on the basis with the electron micrograph.

Titanium oxide is particularly seen the inorganic materials of light-shielding paste as from high whiteness, the viewpoint of covering power, excellent weather resistance, can be fit to use.From the viewpoint of the weather resistance of light-shielding resin, the preferred rutile-type of its crystallization shape.In addition, median size is from the viewpoint to the dispersiveness of resin, preferred 1.0 μ m or below the 1.0 μ m, and comparative optimization 0.8 μ m or below the 0.8 μ m is more preferably 0.4 μ m or below the 0.4 μ m.In addition, from the viewpoint of the power of covering, preferred 0.1 μ m or more than the 0.1 μ m is more preferably 0.2 μ m or more than the 0.2 μ m.Therefore from having both dispersiveness and the viewpoint of covering power, the preferred 0.1 μ m of median size～1.0 μ m.In addition, the median size of titanium oxide is that the basis is measured by image analysis apparatus (Le one ゼッ Network ス IIIU) with the electron micrograph.The titanium oxide of any manufacturing can use in sulfuric acid process and the chlorine method.In addition, better for making with the affinity of resin, also can use hydrous oxide to carry out surface-treated by Al or Si etc.For example, can use the system ィペ one Network R-820 of Ishihara Sangyo Kaisha, Ltd., R-680, CR-50-2, CR-97, CR-60, CR-60-2 etc.

As the use level of the titanium oxide in the light-shielding paste, there is no particular limitation, and preferred usage quantity is 0.1～90 weight % of light-shielding paste total amount of the present invention.From the good viewpoint of coating, preferred usage quantity is 80 weight % of light-shielding paste total amount or 80 weight % are following, comparative optimization 70 weight % or 70 weight % are following, more preferred 50 weight % or 50 weight % are following, preferred especially 40 weight % or below the 40 weight %, preferred more especially 30 weight % or below the 30 weight %.If use level is many, then coating reduces, the tendency that exists opacifying property to be easy to reduce owing to coating is bad.In addition, from the good viewpoint of opacifying property, preferred usage quantity is 5 weight % of light-shielding paste total amount or 5 weight % are above, comparative optimization 10 weight % or 10 weight % are above, more preferred 30 weight % or 30 weight % are above, preferred especially 40 weight % or 40 weight % are above, very preferred 50 weight % or more than the 50 weight %.Therefore, for having both coating and opacifying property, 10 weight %～80 weight %, the comparative optimization 20 weight %～70 weight % that preferred usage quantity scope is the light-shielding paste total amount, be more preferably 30 weight %～60 weight %.

In addition, when using aluminum oxide, silicon-dioxide, boron nitride, aluminium nitride etc., weathering resistance is strengthened, keep high-reflectivity as inorganic materials.

Fluorescent substance as inorganic materials not only has screening effect, and can change the blue light that sends from led chip into white light, and then improves the characteristic of photodiode.In addition, except that fluorescent substance,, can further strengthen directive property by in this light-shielding paste, containing diffusant.Can use the barium titanate, titanium oxide, aluminum oxide, silicon oxide etc. of mineral-type or guanamine resin of organic class etc. as concrete diffusant.Fluorescent substance is to be used for the material that the visible light of will emit from nitride-based compound semiconductor and UV-light change other emission wavelengths into.Therefore, the emission wavelength of the expectation of emitting corresponding to the emission wavelength of the light that sends from the luminescent layer that is used for led chip or from photodiode can use various materials.Especially, the light that sends at led chip and the optical excitation of sending by led chip and from luminous fluorescent substance send only complementary color concerns the time, can send white color system light.

As such fluorescent substance, can enumerate by cerium activated yttrium aluminum garnet class fluorescent substance, Yong perylene analog derivative, by copper, aluminium activated zinc-cadmium sulfide or by manganese activated various materials such as magnesium oxide titanium.These fluorescent substances can use a kind of, also can mix use more than 2 kinds or 2 kinds, especially, because by cerium activated yttrium aluminum garnet class fluorescent substance (Re ₃Re ' ₅O ₁₂: Ce, here, Re is select from Y, Gd, Lu, Sc, La at least a, Re ' is select from Al, In, B, T1 at least a) be garnet structure, therefore heat-resisting, Guang Heshui, the peak value that can make excitation spectrum is near 450nm.In addition, luminescence peak also near 530nm etc., can produce the wide luminescent spectrum that tows to 700nm.And, by replace the part of the Al that forms with Ga, can make emission wavelength to short wavelength's one side shifting, in addition, the part by replacing the Y that forms with Gd can make emission wavelength to long wavelength's one side shifting.Like this, form, can obtain the various emission wavelengths of successive by changing, therefore preferred especially as fluorescent substance.In addition, look expectation, emission wavelength can be regulated to long wavelength or short wavelength, therefore, the part of yttrium can be replaced into Lu, Sc, La, also the some of aluminium can be replaced into In, B, Tl.Have, except that cerium, the Tb or the Cr that contain trace also can adjust absorbing wavelength again.

From the good viewpoint of transformative, the preferred usage quantity of fluorescent substance is 5 weight % of light-shielding paste total amount or more than the 5 weight %, comparatively preferred 10 weight % or more than the 10 weight %, more preferred 30 weight % or more than the 30 weight %, preferred especially 40 weight % or more than the 40 weight %, very preferred 50 weight % or more than the 50 weight %.80 weight % of the preferred light-shielding paste total amount of the upper limit of usage quantity or below the 80 weight % are more preferably 60 weight % or below the 60 weight %.

Below, solidification compound of the present invention is described.

This solidification compound contain contain at least in (A) 1 molecule 2 with the SiH base have the compound that contains silicon compound, (C) hydrosilylation catalysts, (D) silane coupling agent of 2 SiH bases at least in molecule of organic compound, (B) of reactive carbon-to-carbon double bond and/or contain epoxy group(ing), (E) silanol condensation catalyst and (F) inorganic materials as neccessary composition.

At first (A) composition is described.

(A) composition so long as contain at least in 1 molecule 2 with the SiH base to have the organic compound of reactive carbon-to-carbon double bond just passable, have no particular limits.As organic compound, preferably do not contain the such siloxane unit (Si-O-Si) of polysiloxane-organic segmented copolymer or polysiloxane-organic graft copolymer, as component, preferably only contain C, H, N, O, S, halogen.When containing siloxane unit, can produce the problem of gas-premeable or shrinkage cavity (はじ I).

There is no particular limitation to have the bonding position of reactive carbon-to-carbon double bond with the SiH base, and being present in intramolecular any position can.

(A) organic compound of composition can be divided into organic polymer compounds and organic monomer compounds.

As the organic polymer compounds, can use, for example polyethers, polyester, polyarylester class, polycarbonate-based, saturated hydrocarbons, unsaturated hydro carbons, polyacrylate(s), polyamide-based, phenol formaldehyde (PF) class (resol class), polyimide compounds etc.

As the monomer compounds, for example can enumerate, phenols, bisphenols, benzene, naphthalene etc. are aromatic hydrocarbon based; Aliphatic hydrocarbons such as straight chain class, alicyclic ring class; Heterocyclic compound and their mixture etc.

As in (A) composition, having reactive carbon-to-carbon double bond, have no particular limits, but, preferably use following general formula (II) from reactive viewpoint with the SiH base

(in the formula, R ²Expression hydrogen atom or methyl) group of expression.In addition, from the easy degree that raw material obtains, use

The group of expression is preferred especially.

As in (A) composition, having reactive carbon-to-carbon double bond with the SiH base, from the high this point of thermotolerance of cured article, useful following general formula (III) in the preferred ring

(R in the formula ³Expression hydrogen atom or methyl, 2 R ³Can be the same or different.) the ester ring type group of part-structure of expression.In addition, from the easy degree that raw material obtains, useful following general formula in the preferred ring

The ester ring type group of the part-structure of expression.

Having reactive carbon-to-carbon double bond with the SiH group can directly combine with the skeleton part of (A), also can be by divalent or the above substituting group covalent attachment of divalent.

As divalent or the substituting group more than the divalent, so long as that carbonatoms is 0～10 substituting group is just passable, there is no particular limitation, but as constituting element, preferably only contains C, H, N, O, S and halogen.As these substituent examples, can enumerate

-O-，

-S-

CH ₂ _n.

(n represents 1～10 number.)

(n represents 0～4 number.)

(n represents 0～4 number.)

Deng.In addition, the above substituting group of these divalents more than 2 or 2 or divalent also can connect by covalent linkage, constitutes the above substituting group of 1 divalent or divalent.

Example as the group that is covalently bonded in above skeleton part can be enumerated; vinyl, allyl group, methylallyl, acryl, methacryloyl, 2-hydroxyl-3-(allyloxy) propyl group, 2-allyl phenyl, 3-allyl phenyl, 4-allyl phenyl, 2-(allyloxy) phenyl, 3-(allyloxy) phenyl, 4-(allyloxy) phenyl, 2-(allyloxy) ethyl, 2; two (allyloxy methyl) butyl of 2-, 3-allyloxy-2, two (allyloxy methyl) propyl group of 2-,

CH-CH ₂-O _nCH ₂-CH＝CH ₂

(n represents to satisfy the number of 5 〉=n 〉=2.)

(R represents to be selected from-O-,-CH ₂-,

The divalent group.)

(n represents 0～4 number)

Deng.

Object lesson as (A) composition, can enumerate, Phthalic acid, diallyl ester, the trimellitic acid triallyl, glycol ether two (allyl carbonate), trimethylolpropane allyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetraene propoxy-ethane, the diallylidene tetramethylolmethane, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinyl hexanaphthene, (purity is 50～100% to the Vinylstyrene class, preferred purity is 80～100%), divinyl biphenyl, 1, the 3-di isopropenylbenzene, 1, the 4-di isopropenylbenzene, and their oligopolymer, 1,2-polyhutadiene (1,2 ratio is 10～100%, and preferred 1,2 ratio is 50～100%), the allyl ethers of phenolic varnish phenol, allylation polyphenylene oxide;

(R represents to be selected from-O-,-CH ₂-,

The divalent group.)

(n1)

Outside, also have part or all of the epoxypropyl of present known Resins, epoxy replaced with material that allyl group obtains etc.

As (A) composition, also can use to be difficult to show the low-molecular weight compound of dividing into above-mentioned skeleton part and alkenyl.Object lesson as these low-molecular weight compounds, can enumerate, aliphatics ring-type polyenic compounds class, vinyl cyclopentenes, vinyl cyclohexene such as aliphatics chain polyenic compounds class, cyclopentadiene, cyclohexadiene, cyclooctadiene, Dicyclopentadiene (DCPD), three cyclopentadiene, norbornadienes such as divinyl, isoprene, octadiene, decadiene etc. replace aliphatics cyclic olefin compounds etc.

As (A) composition, on the stable on heating viewpoint of further raising, contain with the SiH base in preferred every 1g (A) composition and have reactive carbon-to-carbon double bond 0.001mol or the material more than the 0.001mol, the every 1g of comparative optimization (A) composition contains 0.005mol or the above material of 0.005mol, is more preferably every 1g (A) composition and contains 0.008mol or the above material of 0.008mol.

(A) have the number of reactive carbon-to-carbon double bond as long as have at least 2 in average per 1 molecule with the SiH base in the composition, but when wishing further to improve mechanical strength, preferably, be more preferably more than 3 or 3 above 2.(A) number that per 1 intramolecular and SiH base has reactive carbon-to-carbon double bond in the composition is when 1 or 1 are following, even and (B) the composition reaction also just become Grafting Structure and can not become crosslinking structure.

As (A) composition, from the good viewpoint of reactivity, contain the vinyl more than 1 or 1 in preferred 1 molecule, be more preferably the vinyl that contains in 1 molecule more than 2 or 2.In addition,, contain the vinyl below 6 or 6 in preferred 1 molecule, be more preferably the vinyl that contains in 1 molecule below 4 or 4 from the viewpoint that storage stability becomes good easily.

As (A) composition, little from the stringiness of high viewpoint of mechanics thermotolerance and stock liquid, plasticity, operability, the viewpoint that coating is good, preferred molecular weight less than 900, comparative optimization less than 700, be more preferably less than 500.The viewpoint of and good operability little from volatility more than preferred 100 or 100, is more preferably more than 150 or 150.Molecular weight can be measured by for example gas chromatography mass analyser and liquid chromatography spectrometry mass.

As (A) composition, for obtaining and the uniform mixing of other compositions and good operability, viscosity is preferably at 23 ℃ of following less thaies 1000 pools, is more preferably less than 300 pools, preferred especially less than 30 pools.As lower limit, preferred 0.05 the pool or 0.05 the pool more than, be more preferably 0.1 the pool or 0.1 the pool more than.Viscosity can be measured by E type viscometer.

As (A) composition, from suppressing painted particularly xanthochromic viewpoint, the compounds content that preferably has phenol hydroxyl and/or phenol hydroxy derivatives is few, is more preferably the material that does not contain the compound with phenol hydroxyl and/or phenol hydroxy derivatives.Said phenol hydroxyl is the hydroxyl that directly is combined on the aromatic hydrocarbonss nuclears such as for example phenyl ring, naphthalene nucleus, anthracene nucleus among the present invention, and said phenol hydroxy derivative is the group that the hydrogen atom by above-mentioned phenol hydroxyls of acyl substituted such as alkenyls such as alkyl such as methyl, ethyl, vinyl, allyl group, acetoxyl groups obtains.

Painted few from the light-shielding resin that obtains, the viewpoint that photostabilization is strong, as (A) composition preferred vinyl tetrahydrobenzene, Dicyclopentadiene (DCPD), triallyl isocyanurate, 2, the diallyl ether, 1,2 of two (4-hydroxy-cyclohexyl) propane of 2-, 4-trivinyl hexanaphthene, preferred especially triallyl isocyanurate, 2, the diallyl ether, 1,2 of two (4-hydroxy-cyclohexyl) propane of 2-, 4-trivinyl hexanaphthene.

For reaching the purpose of the viscosity that reduces the solidification compound that obtains, special preferred vinyl tetrahydrobenzene, Vinylstyrene, 1,2,4-trivinyl hexanaphthene, triallyl isocyanurate.

The reactive group that also can have other as (A) composition.As the reactive group of this moment, can enumerate epoxy group(ing), amino, free-radical polymerised unsaturated group, carboxyl, isocyanate group, hydroxyl, alkoxysilyl etc.When having these functional groups, be easy to improve the cementability of the solidification compound that obtains, and be easy to improve the intensity of the cured article that obtains.From the viewpoint that can make cementability become higher, the preferred epoxy group(ing) in these functional groups.In addition, be easy to improve on the thermotolerance this point of the cured article that obtains, preferred average 1 intramolecularly has the reactive group more than 1 or 1.

As (A) composition, it seems from the viewpoint that the thermotolerance photostabilization is high, preferably contain useful following general formula (I)

(in the formula, R ¹Any monovalent organic radical group of expression carbonatoms 1～50, each R ¹Can difference also can be identical) organic compound of expression.

R as above-mentioned general formula (I) ¹, from can so that to the higher viewpoint of thermotolerance of cured article, any monovalent organic radical group of preferred carbonatoms 1～20, any monovalent organic radical group of more preferred carbonatoms 1～10, especially preferably any monovalent organic radical group of carbonatoms 1～4.As R ¹Example can enumerate preferably, methyl, ethyl, propyl group, butyl, phenyl, benzyl, styroyl, vinyl, allyl group, epoxypropyl,

 CH ₂ _nCH ₃(n is 4～19 number in the formula)

 CH ₂ _nCH=CH ₂(n is 2～18 number in the formula)

(n is 0～17 number in the formula)

(n is 0～19 number in the formula)

Deng.

R as above-mentioned general formula (I) ¹, from can so that to cured article and the better viewpoint of cementability of various materials, preferred 3 R ¹In have at least 1 to be that the carbonatoms that contains one or more epoxy group(ing) is 1～50 any monovalent organic radical group, be more preferably contain useful

The carbonatoms that contains one or more epoxy group(ing) of expression is 1～50 any monovalent organic radical group.As these preferred R ¹Example can enumerate epoxypropyl,

(n is 2～18 number in the formula)

Deng

R as above-mentioned general formula (I) ¹From can so that to the viewpoint of chemical heat good stability of cured article, preferred among these at least one to contain the Sauerstoffatom below 2 or 2 and only contain C, H, N, O be 1～50 any monovalent organic radical group as the carbonatoms of component, be more preferably carbonatoms and be 1～50 monovalence alkyl.As these preferred R ¹Example, can enumerate methyl, ethyl, propyl group, butyl, phenyl, benzyl, styroyl, vinyl, allyl group, epoxypropyl,

 CH ₂ _nCH ₃(n is 4～19 number in the formula)

 CH ₂ _nCH=CH ₂(n is 2～18 number in the formula)

(n is 0～17 number in the formula)

(n is 0～19 number in the formula)

Deng.

R as above-mentioned general formula (I) ¹, from the good viewpoint of reactivity, preferred 3 R ¹In have at least 1 to be to contain one or more usefulness

The carbonatoms of group of expression is 1～50 any monovalent organic radical group, is more preferably to contain one or more with following general formula (IV)

(in the formula, R ⁴Expression hydrogen atom or methyl) carbonatoms of group of expression is 1～50 any monovalent organic radical group, preferred especially 3 R ¹In have at least 2 to be can be with following logical formula V

(in the formula, R ⁵The divalent organic group of expression Direct Bonding or carbonatoms 1～48, R ⁶Expression hydrogen atom or methyl) organic compound (a plurality of R of expression ⁵And R ⁶Separately can difference also can be identical).

The R of above-mentioned logical formula V ⁵It is the divalent organic group of Direct Bonding or carbonatoms 1～48, but from can so that to the higher viewpoint of thermotolerance of cured article, the divalent organic group of preferred Direct Bonding or carbonatoms 1～20, be more preferably the divalent organic group of Direct Bonding or carbonatoms 1～10, the divalent organic group of preferred especially Direct Bonding or carbonatoms 1～4.As these preferred R ⁵Example, can enumerate

 CH ₂ _n(n is 0～17 number in the formula)

(n is 0～16 number in the formula)

(n is 0～16 number in the formula)

Deng.

R as above-mentioned logical formula V ⁵From can so that to the viewpoint that has good stability of the chemical heat of cured article, preferred Direct Bonding or contain the Sauerstoffatom below 2 or 2 and only contain C, O, H divalent organic group, the divalent organic group of more preferred Direct Bonding or carbonatoms 1～48 as the carbonatoms 1～48 of component.As these preferred R ⁵Example, can enumerate

 CH ₂ _n(n is 1～17 number in the formula)

(n is 1～16 number in the formula)

(n is 1～16 number in the formula)

Deng.

The R of above-mentioned logical formula V ⁶Be hydrogen atom or methyl, but from the good viewpoint of reactivity, preferred hydrogen atom.

But,, also must contain 2 in 1 molecule at least and have reactive carbon-to-carbon double bond with the SiH group even in the preference of the organic compound of aforesaid general formula (I) expression.From can further improving stable on heating viewpoint, contain the organic compound that has reactive carbon-to-carbon double bond more than 3 or 3 with the SiH group in preferred 1 molecule.

As can be with the preferred object lesson of the organic compound of above-mentioned general formula (I) expression, can enumerate triallyl isocyanurate,

Deng.

For reaching the purpose of the viscosity that reduces the solidification compound that obtains, preferred triallyl isocyanurate.

For improving the cementability of light-shielding resin, as the preferred diallyl list of (A) composition glycidyl chlorinated isocyanurates.

Be raising and the photostabilization that has both the light-shielding resin cementability, as the mixture of preferred triallyl isocyanurate of (A) composition and diallyl list glycidyl chlorinated isocyanurates.Therefore this mixture also is effective from stable on heating viewpoint owing to have chlorinated isocyanurates ring skeleton.Ratio of mixture can be set arbitrarily, but, for achieving the above object preferred triallyl isocyanurate/diallyl list glycidyl chlorinated isocyanurates (mol ratio)=9/1～1/9.Be more preferably 8/2～2/8, preferred especially 7/3～3/7.

(A) composition can use separately, also can use mixing more than 2 kinds or 2 kinds.

Below, (B) composition is described.

(B) of the present invention composition is the compound that contains 2 SiH groups in 1 molecule at least.

For (B) composition, get final product so long as in 1 molecule, contain the compound of 2 SiH groups at least, have no particular limits, for example, can use the compound that contains 2 SiH groups in 1 molecule in the compound that the open WO96/15194 in the world is put down in writing at least etc.

Wherein, from acquired aspect, preferably in 1 molecule, contain the chain and/or the ring-type organopolysiloxane of 2 SiH groups at least.Particularly, can enumerate, for example,

Deng.

From with the good viewpoint of intermiscibility of (A) composition, be more preferably with following general formula (VI)

(in the formula, R ⁷The organic group of expression carbonatoms 1～6, n represents 2～10 number) contain the ring-type organopolysiloxane of 2 SiH groups at least in 1 molecule of expression.

Can be with the substituent R in the compound of following general formula (VI) expression ⁷The preferred organic group of the carbonatoms of being made up of C, H, O 1～6 is more preferably the alkyl of carbonatoms 1～6, special preferable methyl.

As the compound that can use general formula (VI) expression, preferred 1,3,5 from the viewpoint of easy acquisition, the 7-tetramethyl-ring tetrasiloxane.

(B) molecular weight of composition has no particular limits, and can suitably use any molecular weight, but from the viewpoint of the flowability that is easy to show solidification compound more, preferably uses low-molecular-weight.At this moment, the lower limit of molecular weight is preferred 50, and the upper limit of molecular weight is preferred 100,000, is more preferably 1,000, preferred especially 700.

(B) composition can use separately, also the material more than 2 kinds or 2 kinds can be mixed and use.

In addition, from with the good viewpoint of the intermiscibility of (A) composition and be difficult for producing from the volatility of (B) composition and reduce and the viewpoint of the problem that outgases the composition that obtains, (B) composition preferably contains the chain of 2 SiH groups and/or the compound that cyclic polyorganosiloxane (β) obtains by hydrosilylation reactions at least with containing in 1 molecule more than 1 or 1 to have in the organic compound (α) of reactive carbon-to-carbon double bond and 1 molecule with the SiH base.

((α) composition)

Here, as (α) composition can use with 1 molecule as above-mentioned (A) composition in contain 2 at least and have the identical material (α 1) of organic compound of reactive carbon-to-carbon double bond with the SiH base.When using (α 1) composition, the cross-linking density height of the cured article that obtains is easy to obtain the high cured article of mechanical strength.

In addition, also can use and contain 1 in 1 molecule and have the organic compound (α 2) of reactive carbon-to-carbon double bond with the SiH base.When using (α 2) composition, the cured article that obtains is easy to become low elasticity.

((α 2) composition)

As (α 2) composition, has the organic compound of reactive carbon-to-carbon double bond so long as contain 1 in 1 molecule with the SiH base, then have no particular limits, but improving on (B) composition and (A) the composition intermiscibility this point, as compound, preferred polysiloxane-organic segmented copolymer or the polysiloxane-organic graft copolymer such siloxane unit (Si-O-Si) of not containing, and only contain C, H, N, O, S and halogen material as component.

The having the bonding position of reactive carbon-to-carbon double bond with the SiH base there is no particular limitation of (α 2) composition, being present in intramolecular any position can.

The compound of (α 2) composition can be divided into polymer class compound and monomer compounds.

As the polymer class compound, can use for example polysiloxane-based, polyethers, polyester, polyarylester class, polycarbonate-based, saturated hydrocarbons, unsaturated hydro carbons, polyacrylate(s), polyamide-based, phenol formaldehyde (PF) class (resol class), polyimide compounds etc.

In addition, as the monomer compounds, for example can enumerate, phenols, bisphenols, benzene, naphthalene etc. are aromatic hydrocarbon based; The aliphatic hydrocarbon of straight chain class, alicyclic ring class etc.; Heterocyclic compound, silicon compounds and their mixture etc.

As in (α 2) composition, having reactive carbon-to-carbon double bond, have no particular limits, but, preferably use following general formula (II) from reactive viewpoint with the SiH base

(in the formula, R ²Expression hydrogen atom or methyl) group of expression.In addition, from the easy degree that raw material is obtained, especially preferably use

The group of expression.

As have reactive carbon-to-carbon double bond with the SiH base in (α 2) composition, from the high this point of thermotolerance of cured article, having in the preferred ring can be with following general formula (III)

(R in the formula ³Expression hydrogen atom or methyl, 2 R ³Can be the same or different.) the ester ring type group of part-structure of expression.In addition, from the easy degree that raw material obtains, have in the preferred ring and can use following general formula

The ester ring type group of the part-structure of expression.

Having reactive carbon-to-carbon double bond with the SiH group can directly combine with the skeleton part of (α 2) composition, also can be by divalent or the above substituting group covalent attachment of divalent.

As divalent or the substituting group more than the divalent, so long as that carbonatoms is 0～10 substituting group is just passable, have no particular limits, but (B) composition improves this point easily with (A) intermiscibility of composition on, as constituting element, preferably only contain C, H, N, O, S and halogen.As these substituent examples, can enumerate

-O-，

-S-，

(n represents 1～10 number.)

(n represents 0～4 number.)

(n represents 0～4 number.)

Deng.In addition, the above substituting group of these divalents more than 2 or 2 or divalent can connect by covalent linkage, constitutes the above substituting group of 1 divalent or divalent.

Example as the group that is covalently bonded in above these skeleton parts can be enumerated; vinyl, allyl group, methylallyl, acryl, methacryloyl, 2-hydroxyl-3-(allyloxy) propyl group, 2-allyl phenyl, 3-allyl phenyl, 4-allyl phenyl, 2-(allyloxy) phenyl, 3-(allyloxy) phenyl, 4-(allyloxy) phenyl, 2-(allyloxy) ethyl, 2; two (allyloxy methyl) butyl of 2-, 3-allyloxy-2, two (allyloxy methyl) propyl group of 2-,

CH-CH ₂-O _nCH ₂-CH＝CH ₂

(n represents to satisfy the number of 5 〉=n 〉=2.)

(R represents to be selected from-O-,-CH ₂-,

The divalent group.)

(n represents 0～4 number.)

Deng.

Object lesson as (α 2) composition, can enumerate, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-laurylene, 1-hendecene, bright dipping petroleum chemistry society system alkene (Linealene), 4,4-dimethyl-1-amylene, 2-methyl isophthalic acid-hexene, 2,2,4,4-trimethylammonium-chain aliphatic hydrocarbon compounds such as 1-amylene; Annular aliphatic hydrocarbon compound classes such as tetrahydrobenzene, tetrahydrotoluene, methylene radical tetrahydrobenzene, norbornylene, ethylidene tetrahydrobenzene, vinyl cyclohexene, amphene, carene, α-Pai Xi, beta-pinene; Aromatic hydrocarbon based compounds such as vinylbenzene, alpha-methyl styrene, indenes, allyl benzene, 4-phenyl-1-butylene; Allyl ether series, allylin, ethylene glycol monoallyl ether, 4-vinyl-1 such as alkyl allyl ethers, allyl phenyl ether, aliphatic category compounds such as 3-two oxa-s penta ring-2-ketone; 1, aromatic series compounds classes such as 2-dimethoxy-4 '-allyl benzene, o-allyl phenol; Monoene propyl group dibenzyl chlorinated isocyanurates, monoene propyl group diepoxy propyl group chlorinated isocyanurates etc. replace the chlorinated isocyanurates class; Silicon compounds such as vinyl trimethylsilane, vinyltrimethoxy silane, vinyl tri-phenyl-silane etc.In addition, can also enumerate the polyethers resins such as poly(propylene oxide) of the polyethylene oxide of a terminal allylation, a terminal allylation; The hydrocarbon resins such as polyisobutene of a terminal allylation; An end of acrylic resins such as the polymethylmethacrylate of the butyl polyacrylate of a terminal allylation, a terminal allylation etc. contains the polymkeric substance of vinyl or oligopolymer class etc.

Can utilization structure be line style also can be various materials branch-like, that molecular weight also has no particular limits.The distribution of molecular weight also has no particular limits, but on the viewpoint that the viscosity that makes mixture reduces and plasticity improves easily, below the molecular weight distribution preferred 3 or 3, is more preferably below 2 or 2, below preferred especially 1.5 or 1.5.

(α 2) are when there is second-order transition temperature in composition, also there is no particular limitation for it, can use various second-order transition temperatures, but on the cured article that obtains is easy to become strong and unyielding this point, the preferred glass transition temperature is below 100 ℃ or 100 ℃, be more preferably below 50 ℃ or 50 ℃, preferred especially below 0 ℃ or 0 ℃.As the example of preferred resin, can enumerate butyl polyacrylate resin etc.On the contrary, uprise on this point in the thermotolerance that makes the cured article that obtains, the preferred glass transition temperature is more preferably more than 120 ℃ or 120 ℃ more than 100 ℃ or 100 ℃, and is preferred especially more than 150 ℃ or 150 ℃, very preferred more than 170 ℃ or 170 ℃.Second-order transition temperature can be in Measurement of Dynamic Viscoelasticity, obtains tan δ and is shown as the temperature when very big and tries to achieve.

As (α 2) composition, on the thermotolerance this point of the cured article that raising obtains, the preferred hydrocarbons compound.At this moment, preferred carbonatoms lower limit is 7, and the preferred carbonatoms upper limit is 10.

The reactive group that also can have other as (α 2) composition.As the reactive group of this moment, can enumerate epoxy group(ing), amino, free-radical polymerised unsaturated group, carboxyl, isocyanate group, hydroxyl, alkoxysilyl etc.When having these functional groups, be easy to improve the cementability of the solidification compound that obtains, and be easy to improve the intensity of the cured article that obtains.From the viewpoint that can make cementability become higher, the preferred epoxy group(ing) in these functional groups.In addition, be easy to improve on the thermotolerance this point of the cured article that obtains, preferred average 1 intramolecularly has the reactive group more than 1 or 1.Particularly, can enumerate monoene propyl group diepoxy propyl group chlorinated isocyanurates, allyl group glycidyl ethers, allyloxy ethyl methacrylic ester, allyloxy ethyl acrylate, vinyltrimethoxy silane etc.

Can use one matter as above-mentioned (α 2) composition, also a plurality of combinations of substances can be used.

((β) composition)

(β) composition is chain and/or the cyclic polyorganosiloxane that contains 2 SiH groups in 1 molecule at least.Particularly, can enumerate, for example,

Deng.

Here, be easy to the viewpoint that becomes good, be more preferably with following general formula (VI) from intermiscibility with (α) composition

(in the formula, R ⁷The organic group of expression carbonatoms 1～6, n represents 3～10 number) contain the cyclic polyorganosiloxane of 3 SiH groups at least in 1 molecule of expression.

Can use the substituent R in the compound of general formula (VI) expression ⁷The preferred organic group of the carbonatoms 1～6 that is made of C, H, O is more preferably the alkyl of carbonatoms 1～6, special preferable methyl.

From the viewpoints of obtaining such as easiness, preferred 1,3,5, the 7-tetramethyl-ring tetrasiloxane.

Above-mentioned various (β) composition can use separately, also material more than 2 kinds or 2 kinds can be mixed and use.

((α) composition and (β) reaction of composition)

Below, to use can be by (α) composition and (β) (α) composition the when compound that obtains by hydrosilylation reactions of composition is as (B) of the present invention composition and (β) hydrosilylation reactions of composition describe.

In addition, (α) composition and (β) when composition carries out hydrosilylation reactions, can obtain comprising the mixture of a plurality of compounds of (B) of the present invention composition, but can directly use mixture to make solidification compound of the present invention from wherein isolating (B) composition.

(α) composition and (β) (α) composition when composition carries out hydrosilylation reactions and (β) blending ratio of composition have no particular limits, but considering by (B) composition that obtains with (A) during the intensity of the cured article that obtains of the hydrosilylation of composition, because (B) SiH Quito of composition is preferred, therefore, usually, has the ratio of the sum (Y) of the sum (X) of the carbon-to-carbon double bond of reaction and the SiH base in blended (β) composition with the SiH base in blended (α) composition, preferred Y/X 〉=2 are more preferably Y/X 〉=3.In addition, from being easy to make (B) composition and (A) the better this point of intermiscibility of composition, preferred 10 〉=Y/X is more preferably 5 〉=Y/X.

(α) composition and (β) when composition carries out hydrosilylation reactions also can use suitable catalyzer, as catalyzer, can use for example following hydrosilylation catalysts.Can enumerate, solid platinum is carried on the coordination compound of the material, Platinic chloride, Platinic chloride and the alcohol that obtain on the carriers such as platinum simple substance, aluminum oxide, silicon-dioxide, carbon black, aldehyde, ketone etc., platinum-olefin(e)complex (for example, Pt (CH ₂=CH ₂) ₂(PPh ₃) ₂, Pt (CH ₂=CH ₂) ₂Cl ₂), platinum-vinylsiloxane coordination compound (Pt (ViMe for example ₂SiOSiMe ₂Vi) _n, Pt[(MeViSiO) ₄] _m), platinum-phosphine coordination compound (for example, Pt (PPh ₃) ₄, Pt (PBu ₃) ₄), platinum-phosphite coordination compound (for example, Pt[P (OPh) ₃] ₄, Pt[P (OBu) ₃] ₄) (in the formula, Me represents that methyl, Bu represent that butyl, Vi represent that vinyl, Ph represent phenyl, and n, m represent integer), the pure platinum catalyst put down in writing in No. 3220972 specification sheets of United States Patent (USP) of platinum-hydrocarbon complex body of putting down in writing in No. the 3159601st, the United States Patent (USP) of dicarbapentaborane platinum dichloride, Karstedt catalyzer, Ashby and No. 3159662 specification sheets, Lamoreaux etc.Have, platinum chloride-alkene complex body of putting down in writing in No. 3516946 specification sheets of the United States Patent (USP) of Modic also is useful in the present invention again.

In addition, as the example of the catalyzer beyond the platinic compound, can enumerate RhCl (PPh) ₃, RhCl ₃, RhAl ₂O ₃, RuCl ₃, IrCl ₃, FeCl ₃, AlCl ₃, PdCl ₂2H ₂O, NiCl ₂, TiCl ₄Deng.

In these, from catalyst activity, preferred Platinic chloride, platinum-olefin(e)complex, platinum-vinylsiloxane coordination compound etc.In addition, these catalyzer can use separately, also can use simultaneously more than 2 kinds or 2 kinds.

There is no particular limitation for the addition of catalyzer, and for having sufficient solidified nature and the cost of solidification compound is suppressed at lower level, the lower limit of preferred addition is that the SiH base with respect to 1 mole of (β) composition is 10 ^-8Mole is more preferably 10 ^-6Mole, the upper limit of preferred addition are that the SiH base with respect to 1 mole of (β) composition is 10 ^-1Mole is more preferably 10 ^-2Mole.

In addition, can in above-mentioned catalyzer, use promotor simultaneously.For example can enumerate Phosphorus compound such as triphenylphosphine as promotor; Dimethyl maleate etc. 1,2-two ester compounds; Alkynol compounds such as 2-hydroxy-2-methyl-ethyl acetylene; Sulphur compounds such as elemental sulfur; Aminated compoundss such as triethylamine etc.

There is no particular limitation for the addition of promotor, but for 1 mole of hydrosilylation catalysts, be limited to 10 under the preferred addition ^-2Mole, more preferred 10 ^-1Mole is limited to 10 on the preferred addition ²Mole, more preferred 10 moles.

Blending means as when reaction (α) composition, (β) composition, catalyzer can adopt the whole bag of tricks, but the material that preferably will mix catalyzer in (α) composition is mixed into the method in (β) composition.Employing to (α) composition with (β) during the method in the mixture of ingredients, is difficult to the control reaction with catalyst mix.When taking that (α) composition is mixed into method in the material after (β) composition and the catalyst mix, because catalyzer exists down, (β) composition and the moisture of sneaking into have reactivity, therefore can produce rotten.

Can be set at all temps as temperature of reaction, but this moment, the lower limit of preferred temperature of reaction is 30 ℃, is more preferably 50 ℃, the upper limit of preferred temperature of reaction is 200 ℃, is more preferably 150 ℃.Temperature of reaction is low, can prolong the reaction times that reaches abundant reaction, and the temperature of reaction height then is unpractical.Reaction can be carried out at a certain temperature, but optionally also can the multistage or transformation temperature continuously.

Pressure when reaction times, reaction also can carry out multiple setting as required.

Also can use solvent during hydrosilylation reactions.Operable solvent only otherwise hindering hydrosilylation reactions gets final product, there is no particular limitation, as concrete example, can use varsols such as benzene, toluene, hexane, heptane; Tetrahydrofuran (THF), 1,4-diox, 1, ether solvents such as 3-two oxa-s penta ring, ether; Ketones solvent such as acetone, methylethylketone; Chloroform, methylene dichloride, 1, halogen solvents such as 2-ethylene dichloride.This solvent can use separately, also can mix use more than 2 kinds or 2 kinds.As solvent, preferred toluene, tetrahydrofuran (THF), 1,3-two oxa-s penta ring, chloroform.The quantity of solvent of using also can suitably be set.

In addition, in order to reach the reactive purpose of control etc., can also use various additives.

(α) composition and (β) after the composition reaction, can with solvent and/or unreacted (α) composition and/or (β) composition remove.By removing these volatile components, do not contain volatile component in (B) composition that obtains, therefore when solidifying, be difficult for producing owing to the space that the volatile component volatilization causes, the problem of crackle with (A) composition.As the method for removing, can enumerate, for example except that decompression devolatilization composition, handle by gac, pure aluminium silicate, silica gel etc. etc.Preferred subzero treatment when decompression devolatilization composition.This moment, preferred upper temperature limit was 100 ℃, was more preferably 60 ℃.If at high temperature handle easily with the tackify iso-metamorphism.

As above conduct (α) composition and (β) example of (B) composition of the reaction product of composition, can enumerate Vinylstyrene and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, dihydroxyphenyl propane diallyl ether and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, vinyl cyclohexene and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, Dicyclopentadiene (DCPD) and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, triallyl isocyanurate and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, diallyl list glycidyl chlorinated isocyanurates and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, glycidyl allyl ether and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, alpha-methyl styrene and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, monoene propyl group Diglycidylisocyanury-ester and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane etc.

From the low viscous viewpoint of solidification compound, preferred Vinylstyrene and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, alpha-methyl styrene and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane.

From the sunproof viewpoint of thermotolerance of the resin that obtains after solidification compound solidifies, preferred Vinylstyrene and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane and triallyl isocyanurate and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane.In addition, from the viewpoint of thermotolerance photostabilization cementability, preferred diallyl list glycidyl chlorinated isocyanurates and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane, monoene propyl group Diglycidylisocyanury-ester and 1,3,5, the reactant of 7-tetramethyl-ring tetrasiloxane.

Below, the hydrosilylation catalysts as (C) of the present invention composition is described.

As hydrosilylation catalysts, as long as have the catalyst activity of hydrosilylation reactions, there is no particular limitation, can enumerate, for example solid platinum is carried on the coordination compound of the material, Platinic chloride, Platinic chloride and the alcohol that obtain on the carriers such as platinum monomer, aluminum oxide, silicon-dioxide, carbon black, aldehyde, ketone etc., platinum-olefin(e)complex (for example, Pt (CH ₂=CH ₂) ₂(PPh ₃) ₂, Pt (CH ₂=CH ₂) ₂Cl ₂), platinum-vinylsiloxane coordination compound (Pt (ViMe for example ₂SiOSiMe ₂Vi) _n, Pt[(MeViSiO) ₄] _m), platinum-phosphine coordination compound (for example, Pt (PPh ₃) ₄, Pt (PBu ₃) ₄), platinum-phosphite coordination compound (for example, Pt[P (OPh) ₃] ₄, Pt[P (OBu) ₃] ₄) (in the formula, Me represents that methyl, Bu represent that butyl, Vi represent that vinyl, Ph represent phenyl, and n, m represent integer), the pure platinum catalyst put down in writing in No. 3220972 specification sheets of United States Patent (USP) of platinum-hydrocarbon complex body of putting down in writing in No. the 3159601st, the United States Patent (USP) of dicarbapentaborane platinum dichloride, Karstedt catalyzer, Ashby and No. 3159662 specification sheets, Lamoreaux etc.Have, platinum chloride-alkene complex body of putting down in writing in No. 3516946 specification sheets of the United States Patent (USP) of Modic also is useful in the present invention again.

There is no particular limitation for the addition of catalyzer, and for having sufficient solidified nature and the cost of solidification compound is suppressed at lower level, the lower limit of preferred addition is that the SiH base with respect to 1 mole of (B) composition is 10 ^-8Mole is more preferably 10 ^-6Mole, the upper limit of preferred addition are that the SiH base with respect to 1 mole of (B) composition is 10 ^-1Mole is more preferably 10 ^-2Mole.

In addition, this hydrosilylation catalysts, owing to be used in (B) composition remaining amount when synthetic, thus when showing sufficient solidified nature, then needn't add, but for adjusting solidified nature, also can add again in above-mentioned scope.

In addition, can and use promotor in above-mentioned catalyzer.For example can enumerate Phosphorus compound such as triphenylphosphine as promotor; Dimethyl maleate etc. 1,2-two ester compounds; Alkynol compounds such as 2-hydroxy-2-methyl-ethyl acetylene; Sulphur compounds such as free sulfur; Aminated compoundss such as triethylamine etc.

For purpose that reaches the storage stability of improveing the present composition or the reactive purpose that is adjusted at the hydrosilylation reactions in the manufacturing processed, can use cure retarder.As cure retarder, can enumerate, contain compound, organo phosphorous compounds, organosulfur compound, nitrogenous compound, tin compound, organo-peroxide of aliphatics unsaturated link(age) etc., also can use them simultaneously.

As the compound that contains the aliphatics unsaturated link(age), can enumerate propiolic alcohol, eneyne compounds, maleic acid ester class etc.As organo phosphorous compounds, can enumerate three organic radical phosphine classes, two organic radical phosphine classes, organic radical phosphine class, three organic phosphites etc.Can enumerate organosulfur alcohols, two organosulfur ethers, hydrogen sulfide, benzothiazole, thiazole, benzothiazyl disulfide etc. as organosulfur compound.As nitrogenous compound, can enumerate ammonia, 1～3 grade of alkyl amine, arylamine class, urea, hydrazine etc.As tin compound, can enumerate inferior tin 2 hydrates of halogenation, the inferior tin of carboxylic acid etc.Can enumerate ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide, the perbenzoic acid tert-butyl ester etc. as organo-peroxide.

In these cure retarder, from delaying the viewpoint that activity is good, raw material obtains easily, preferred benzothiazole, thiazole, dimethyl maleate, 3-hydroxy-3-methyl-ethyl acetylene, 1-ethynyl-1-hexalin.

The addition of cure retarder can be set at multiple, but for the 1mol hydrosilylation catalysts that uses, the lower limit of preferred addition is 10 ^-1Mole, more preferred 1 mole, the upper limit of preferred addition is 10 ³Mole, more preferred 50 moles.

In addition, these cure retarder can be used separately, also can use simultaneously more than 2 kinds or 2 kinds.

Below, to describing as the silane coupling agent of (D) composition and/or the compound that contains epoxy group(ing).(D) of the present invention composition by with (E) of the present invention composition combination, be necessary as the composition of giving to solidification compound with the cementability of shell resin.

As silane coupling agent, have reactive functional group and water-disintegrable silicon group is just passable so long as have one in the molecule respectively at least with organic group, there is no particular limitation.

As having reactive functional group with organic group; viewpoint from operability; preferred at least one functional group of from epoxy group(ing), methacryloyl, acryl, isocyanate group, tricarbimide ester group, vinyl, carbamate groups, selecting; viewpoint from solidified nature and cementability; be more preferably epoxy group(ing), methacryloyl, acryl, preferred especially epoxy group(ing).

As water-disintegrable silicon group, from the viewpoint of operability, preferred alkoxysilyl, from reactive viewpoint, preferred especially methoxy methyl silylation, (ethoxymethyl) silylation.

As preferred silane coupling agent, can give an example out, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane etc. have the alkoxyl silicone alkanes of epoxy-functional; 3-methyl allyl acyloxypropyl trimethoxysilane, 3-methacryloxypropyl triethoxyl silane, 3-acryloyl-oxy propyl trimethoxy silicane, 3-acryloyl-oxy propyl-triethoxysilicane, methacryloxypropyl methyltrimethoxy silane, methacryloxypropyl Union carbide A-162, acryloyl-oxy methyltrimethoxy silane, acryloyl-oxy Union carbide A-162 etc. have the alkoxyl silicone alkanes of methacryloyl or acryl.

Addition as silane coupling agent can be set at multiple, but for 100 weight parts [(A) composition+(B) composition], preferred addition lower limit is 0.1 weight part, more preferred 0.5 weight part, the upper limit of preferred addition is 50 weight parts, more preferred 25 weight parts.If, then there is the unfavorable tendency of improved in adhesion effect less than 0.1 weight part in addition, addition is greater than 50 weight parts, the tendency that then exists the cured article rerum natura to be easy to reduce.

As the compound that the contains epoxy group(ing) various Resins, epoxy of can giving an example out.As Resins, epoxy, can enumerate, for example, with phenolic varnish phenol type Resins, epoxy, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin, the Bisphenol F diglycidylether, bisphenol A diglycidyl ether, 2,2 '-two (4-glycidoxypropyl cyclohexyl) propane, 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, the vinyl cyclohexene dioxide, 2-(3, the 4-epoxycyclohexyl)-5,5-spiral shell-(3, the 4-epoxy cyclohexane)-1, the 3-diox, two (3, the 4-epoxycyclohexyl) adipic acid ester, 1,2-cyclopropane dicarboxylic acid bisglycidyl ester, isocyanuric acid three-glycidyl ester, monoene propyl group Diglycidylisocyanury-ester, Resins, epoxy such as single glycidyl diallyl chlorinated isocyanurates are used hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, the trialkyl Tetra Hydro Phthalic Anhydride, hydrogenation methyl carbic anhydride aliphatic anhydride such as (water elementization メチ Le Na ヅック Suan No water things) is solidified the material that obtains.The independent respectively separately use of these Resins, epoxy or stiffening agent also can a plurality ofly be used in combination.

Addition as the compound that contains epoxy group(ing) can be set at multiple, but for 100 weight parts [(A) composition+(B) composition], preferred addition lower limit is 0.1 weight part, more preferred 0.5 weight part, the upper limit of preferred addition is 50 weight parts, more preferred 25 weight parts.If, then there is the unfavorable tendency of improved in adhesion effect less than 0.1 weight part in addition, addition is greater than 50 weight parts, the tendency that then has the cured article rerum natura to be easy to reduce.

Above-mentioned silane coupling agent, the compound that contains epoxy group(ing) can use separately, also can use simultaneously more than 2 kinds or 2 kinds.

Below, the silanol condensation catalyst of (E) composition is described.(E) of the present invention composition is necessary by making up with (D) of the present invention composition as the composition of giving cementability to solidification compound.

There is no particular limitation as silanol condensation catalyst, but can preferably enumerate organo-aluminium compound, boric acid ester, titanium compound etc.More preferably have machine aluminium compound, boric acid ester.In addition, when solidifying and the low viewpoint of tint permanence at high temperature, the preferred boric acid ester.

Usage quantity when using silanol condensation catalyst can be set at multiple, but for 100 weight parts [(A) composition+(B) composition], preferred addition lower limit is 0.05 weight part, more preferred 0.1 weight part, the upper limit of preferred addition is 50 weight parts, more preferred 30 weight parts.If, then there is the unfavorable tendency of improved in adhesion effect less than 0.05 weight part in addition, addition then exists and brings dysgenic tendency for easily the cured article rerum natura greater than 50 weight parts.

In the present invention, cementability is improved and/or stabilization as the employed organo-aluminium compound of silanol condensation catalyst.

Can enumerate the alkoxide cpd of aluminium such as aluminum methylate, aluminum ethylate, aluminium isopropoxide, three positive propoxy aluminium as being used in organo-aluminium compound of the present invention; The organic acid salt of aluminium such as aluminum napthenate, aluminum stearate, aluminium octoate, M-nitro benzoic acid aluminium; Methyl aceto acetate aluminum-diisopropoxide, methyl aceto acetate two isobutanol aluminums, three (methyl aceto acetates) close that aluminium, ethyl-diacetyl-acetate single acetyl acetone close aluminium, tri acetylacetonato closes chelate compound of aluminium such as aluminium etc., from reactive, with the viewpoint of the bonding adaptation of body material, the chelate compound of preferred aluminium, the alkoxide cpd of aluminium are more preferably the chelate compound of aluminium.Have again, from the chemical compatibility of hydrosilylation cure reaction, preferred three (methyl aceto acetates) close aluminium.This organo-aluminium compound can use separately also and can use simultaneously more than 2 kinds or 2 kinds.

As the employed boric acid ester of silanol condensation catalyst, can improve cementability and/or stabilization in the present invention.

Can use with following general formula (VII), (VIII) expression suitably as the boric acid ester that uses among the present invention

B(OR ⁸) ₃(VII)

B(OCOR ⁸) ₃(VIII)

(in the formula, R ⁸The organic group of expression carbonatoms 1～48).

Object lesson as boric acid ester, can enumerate boric acid three-2-ethylhexyl ester, boric acid three Octadecane esters, boric acid three n-octyls, triphenyl borate, trimethylene boric acid ester, three (trimethyl silyl) boric acid ester, tri-n-butyl borate, boric acid three secondary butyl esters, boric acid three tert-butyl esters, triisopropyl borate ester, boric acid three n-propyls, boric acid triallyl, triethyl borate, trimethyl borate, methyl cellosolve boron etc.1 kind can be only used as boric acid ester, also use can be mixed more than 2 kinds or 2 kinds.Mix when using more than 2 kinds or 2 kinds, mixing can be carried out in advance, also can mix when cured article is made.

Preferred boric acid three Octadecane esters, boric acid three n-octyls, tri-n-butyl borate, triisopropyl borate ester, boric acid three n-propyls, triethyl borate and trimethyl borate.

From acquired this point, preferred boric acid trimethyl, triethyl borate, tri-n-butyl borate are more preferably trimethyl borate.

Volatility from can suppress to solidify the time, be more preferably boric acid three Octadecane esters, boric acid three n-octyls, triphenyl borate, trimethylene boric acid ester, three (trimethyl silyl) boric acid ester, tri-n-butyl borate, boric acid three secondary butyl esters, boric acid three tert-butyl esters, triisopropyl borate ester, boric acid three n-propyls, boric acid triallyl, methyl cellosolve boron, special preferred boric acid three Octadecane esters, boric acid three tert-butyl esters, triphenyl borate, tri-n-butyl borate.

From volatile inhibition, operability, be more preferably tri-n-butyl borate, triisopropyl borate ester, boric acid three n-propyls, special preferred boric acid tri-n-butyl.

Low this of tint permanence under high temperature put, and is more preferably trimethyl borate, triethyl borate, special preferred boric acid trimethyl.

The titanium compound that uses as silanol condensation catalyst can make cementability improve and/or stabilization in the present invention.

As the titanium compound that uses among the present invention, can give an example four titan-alkoxide classes such as tetraisopropoxy titanium, four titanium butoxide; The inner complex class of titaniums such as tetrem acyl pyruvic acid titanium; Has the general titanic acid ester coupler of residues such as oxyacetic acid or ethylene glycol etc.This titanium compound can use separately, also can use simultaneously more than 2 kinds or 2 kinds.

Owing to show cementability, as the silane coupling agent of (D) composition of the present invention's record and/or contain the compound of epoxy group(ing) and all be necessary as the silane condensation catalyzer of (E) composition, any one can not show cementability.

In the present invention,, can also use the silanol source compound, cementability is improved and/or stabilization for further improving the cementability improved effect.As such silanol source compound, can enumerate, for example, alkoxyl silicone alkanes such as silanol compound, dimethoxydiphenylsilane, tetramethoxy-silicane, methyltrimethoxy silanes such as tri-phenyl-silane alcohol, phenylbenzene dihydroxyl silane etc.

Usage quantity when using the silanol source compound can be set at multiple, but for 100 weight part couplers and/or contain the compound of epoxy group(ing), preferred addition lower limit is 0.05 weight part, more preferred 1 weight part, the upper limit of preferred addition is 50 weight parts, more preferred 30 weight parts.If addition, then has the inadequate tendency of improved in adhesion effect less than 0.05 weight part, then there is the cured article rerum natura tendency of reduction easily in addition greater than 50 weight parts.

In addition, these silanol source compounds can use separately, also can use simultaneously more than 2 kinds or 2 kinds.

For improving the coupler among the present invention or containing the effect of the compound of epoxy group(ing), can use carboxylic-acid and/or anhydrides, cementability is improved and/or stabilization.Have no particular limits as such carboxylic-acid, anhydrides, but can enumerate

CH ₃CH ₂ _nCOOH，HOOCCH ₂ _nCOOH

CH ₂=CH  CH ₂ _nCOOH, (n represents 0～30 number.)

, 2 ethyl hexanoic acid, hexahydrobenzoic acid, cyclohexane dicarboxylic acid, methylcyclohexane dicarboxylic acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid, methyl-4-norborneol-1,2-diacid (acid of メチ Le Ha ィミ Star Network), norbornane dicarboxylic acid, hydrogenation methyl Na Dike acid, toxilic acid, acetylenedicarboxylic acid, lactic acid, oxysuccinic acid, citric acid, tartrate, M-nitro benzoic acid, Para Hydroxy Benzoic Acid, TRANSCINNAMIC ACID, phthalic acid, trimellitic acid, pyromellitic acid, naphthalene monocarboxylic acid, naphthalene dicarboxylic acids etc. and they are separately or compound acid anhydrides etc.

In these carboxylic-acids and/or anhydrides, little in the possibility that has hydrosilylation reactions, from cured article, ooze out, be difficult on this aspect of rerum natura of the cured article that infringement obtains, preferably contain with the SiH base and have reactive carbon-to-carbon double bond.As preferred carboxylic-acid and anhydrides, for example can enumerate,

CH ₂=CH  CH ₂ _n(n represents 0～30 number to COOH.)、

Tetrahydrophthalic acid, methyl tetrahydrophthalic acid and they are separately or compound acid anhydrides etc.

Usage quantity when using carboxylic-acid and/or anhydrides can be set at multiple, but with respect to 100 weight part couplers and/or contain the compound of epoxy group(ing), preferred addition lower limit is 0.1 weight part, more preferred 1 weight part, the upper limit of preferred addition is 50 weight parts, more preferred 10 weight parts.If, then there is the inadequate tendency of improved in adhesion effect less than 0.1 weight part in addition, then there is the cured article rerum natura tendency of reduction easily in addition greater than 50 weight parts.

In addition, these carboxylic-acids and/or anhydrides can be used separately, also can use simultaneously more than 2 kinds or 2 kinds.

For purpose that reaches the storage stability of improveing solidification compound of the present invention or the reactive purpose that is adjusted at the hydrosilylation reactions in the manufacturing processed, can use cure retarder.As cure retarder, can enumerate, contain compound, organo phosphorous compounds, organosulfur compound, nitrogenous compound, tin compound, organo-peroxide of aliphatics unsaturated link(age) etc., also can use them simultaneously.

As the compound that contains the aliphatics unsaturated link(age), can enumerate propiolic alcohol, eneyne compounds, maleic acid ester class etc.As organophosphorus compound, can enumerate three organic phosphine classes, two organic phosphine classes, organic phosphine class, three organic phosphites etc.Can enumerate organic mercaptan, two organic thioethers, hydrogen sulfide, benzothiazole, thiazole, benzothiazyl disulfide etc. as organosulfur compound.As nitrogenous compound, can enumerate ammonia, 1～3 grade of alkyl amine, arylamine class, urea, hydrazine etc.As tin compound, can enumerate inferior tin 2 hydrates of halogenation, the inferior tin of carboxylic acid etc.Can enumerate ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide, the perbenzoic acid tert-butyl ester etc. as organo-peroxide.

In these cure retarder, from postponing the viewpoint that activity is good, raw material obtains easily, preferred benzothiazole, thiazole, dimethyl maleate, 3-hydroxy-3-methyl-ethyl acetylene, 1-ethynyl-1-hexalin.

The addition of cure retarder can be set at multiple, but with respect to the 1mol hydrosilylation catalysts that uses, the lower limit of preferred addition is 10 ^-1Mole, more preferred 1 mole, the upper limit of preferred addition is 10 ³Mole, more preferred 50 moles.

Below, as the inorganic materials of (F) composition, can suitably use the material same with above-mentioned inorganic materials.As the use level of the inorganic materials of (F) composition, there is no particular limitation, and preferred usage quantity is 0.1～90 weight % of solidification compound total amount of the present invention.From the good viewpoint of coating, preferred usage quantity is 80 weight % of solidification compound total amount or 80 weight % are following, comparative optimization 70 weight % or 70 weight % are following, more preferred 50 weight % or 50 weight % are following, preferred especially 40 weight % or below the 40 weight %, very preferred 30 weight % or below the 30 weight %.If use level is many, then coating reduces, because the tendency that the bad existence of coating makes opacifying property be easy to reduce.In addition, from the good viewpoint of opacifying property, preferred usage quantity is 5 weight % of solidification compound total amount or 5 weight % are above, comparative optimization 10 weight % or 10 weight % are above, more preferred 30 weight % or 30 weight % are above, preferred especially 40 weight % or 40 weight % are above, very preferred 50 weight % or more than the 50 weight %.Therefore, for having both coating and opacifying property, 10 weight %～80 weight %, the comparative optimization 20 weight %～70 weight % that preferred usage quantity scope is the solidification compound total amount, be more preferably 30 weight %～60 weight %.

Then, in solidification compound of the present invention,, preferably further contain (G) silicon-dioxide except above-mentioned (A)～(F) composition.Silicon-dioxide as (G) composition is described.

As silicon-dioxide, can enumerate, for example thermal silica, settleability silicon-dioxide, quartz, anhydrous silicic acid, fused silica, crystallinity silicon-dioxide, ultra-fine soft silica etc.

Silicon-dioxide is given the solidification compound thixotropy, in addition, can give the tackify effect.As this silicon-dioxide, the preferred 3～20nm of the median size of primary particle, preferred especially 5～10nm.The median size of silicon-dioxide can be basic calculation with the electron micrograph.

From giving thixotropic viewpoint, preferably do not carry out surface treatment.As this silicon-dioxide, can suitably use AEROSIL 300,130,200 that for example Japanese ァェロジ Le Co., Ltd. makes etc.

From the viewpoint of tackify effect, preferably carry out surface treatment.AEROSIL R812, R972, R974, R976, RX200, the RX300 etc. that can suitably use for example Japanese ァェロジ Le Co., Ltd. to make as this silicon-dioxide.

As surface treatment, can enumerate alkylation processing, trimethyl silyl processing, polysiloxane and handle, handle etc. by coupler.

As the example of coupler at this moment, can enumerate silane coupling agent.As silane coupling agent, have reactive functional group and water-disintegrable silicon group is just passable so long as have one in the molecule respectively at least with organic group, there is no particular limitation.

As having reactive functional group with organic group; viewpoint from operability; preferred at least one functional group of from epoxy group(ing), methacryloyl, acryl, isocyanate group, tricarbimide ester group, vinyl, carbamate groups, selecting; from the viewpoint of solidified nature and cementability, preferred especially epoxy group(ing), methacryloyl, acryl.As water-disintegrable silicon group, from the viewpoint of operability, preferred alkoxysilyl, from reactive this point, preferred especially methoxy methyl silylation, (ethoxymethyl) silylation.

There is no particular limitation for the amount of the silicon-dioxide in the solidification compound, but viewpoint from coating and low flow, with respect to resinous principle [(A) composition～(E) composition] 100 weight parts, preferred 0.5 weight part～20 weight parts, be more preferably 2 weight parts～10 weight parts, preferred especially 3 weight parts～5 weight parts.

Then, in solidification compound of the present invention, curtain coating under 100 ℃ on the glass basis material of the angles of 80 degree that tilt after 1 hour, preferred 2cm or 2cm are following.In addition, more preferred 1cm or 1cm are following.

This curtain coating is measured particularly in accordance with the following methods.At first, go up apart from the position of the about 1cm in limit of sheet glass at the thick sheet glass of 10cm * 10cm * 3cm (general blue sheet glass), the solidification compound coating of the present invention of about 150mg is circular.As top, the angle of 80 degree that tilt also is arranged in the baking oven that is heated to 100 ℃ with this sheet glass coated portion.After 1 hour, be the distance that unit measures solidification compound mobile front end and coating position with cm.

Below, the modulator approach of solidification compound of the present invention is described.

The solidification compound that contains above-mentioned (A)～(F) composition can make by mixing these compositions.As the blended method, can adopt the whole bag of tricks, but preferably will mix (A) composition, (C) composition and (E) material that obtains of composition mix remix (F) composition afterwards mutually with the material that mixing (B) composition, (D) composition obtain.If, the tendency that is difficult to control reaction is arranged then to (A) composition and the method for (B) mixing (C) composition in the mixture of ingredients.Mix (B) composition and (C) composition or (E) material that obtains of composition in the presence of (C) composition, (E) composition, can promote the reaction of (B) composition and water, therefore may storage medium can take place rotten,

When composition reacts and solidifies, can take following method: (A), (B), (C), (D), (E) each composition necessary amounts mixed once separately can be reacted, also can mix after a part reacts, add (F) composition, the remix residual content, the further method of reaction or after mixing, by the control reaction conditions or utilize the difference of substitution reaction, after only the part of the functional group in the composition being reacted (B levelization), form to wait and handle and further solidified method.By these methods, adjust the viscosity when being shaped easily.

(F) composition and (A)～(E) blending means of composition for example can to use three-roller, paint grinder mill, ball mill etc. to carry out mixing, mixing back can obtain the light-shielding paste of excellent dispersion by vacuum defoamation.In addition, if 10g or 10g be following a small amount of, can use planetary stirring deaeration machine to stir.

In addition, except that (A)～(F) composition, when further being contained the solidification compound of (G) composition, preferably with (A) composition, (C) composition and (E) composition mix the material that obtains and will (B) composition (D) composition mix the material that obtains mix after, in this mixture, mix (F) composition and (G) composition again.

To mixing (A) composition, (C) composition and (E) mixing (F) composition and (G) during composition in the material that composition obtains, there is viscosity to rise the tendency of operation decline.In addition, will mix (A) composition, (C) composition and (E) mixture of ingredients and (F) composition mixing, and will mix (B) composition, (D) mixture of ingredients and (G) composition mixing, when again the material that obtains being mixed, the tendency of curtain coating increase arranged.In addition, mix (F) composition and (G) composition in (B) composition (D) mixture of ingredients, the material that obtains and (A) composition, (C) composition and (E) during the mixture of ingredients phase mixture have the tendency of curtain coating increase.

Then, illustrate that (A)～(E) mixture of ingredients becomes phase-splitting blended method with (F) composition with (G).Mixing device can suitably use spatula, planetary stirring deaeration machine, dissolver, three-roller, paint grinder mill, ball mill etc.Also can heat during mixing in the temperature/time range that is not cured.Particularly, preferred 70 ℃/3 hours or 70 ℃/below 3 hours.Heating can be in air, or for example implements in the non-active gas such as nitrogen, argon gas.In addition, carry out the solidification compound that vacuum defoamation can obtain excellent dispersion by planetary stirring deaeration machine, dissolver.In addition, be the purpose of the proterties stabilization that reaches the solidification compound that mixing is obtained, the slaking of can heating.Particularly,, carry out more than 1 hour or 1 hour, be more preferably under 50 ℃, carry out about 2 hours preferably 40 ℃～60 ℃ temperature range.

Solidification compound of the present invention can be pre-mixed as above-mentioned, and solidifies by part or all reaction that has reactive carbon-to-carbon double bond and a SiH base with the SiH base in the composition, obtains cured article.

In addition, light-shielding paste of the present invention comprises above-mentioned solidification compound.

Light-shielding paste of the present invention can be pre-mixed as above-mentioned, and by having part or all reaction and the curing of reactive carbon-to-carbon double bond and SiH base with the SiH base in the composition, obtains light-shielding resin.

As this light-shielding paste is solidified the method that obtains the light-shielding resin layer on by article attaching, only can use and react with the blended method, also can heat and react.From reacting fast, the common viewpoint that obtains the high material of thermotolerance easily, the method that preferred heating is reacted.

Temperature as reaction can be set at multiplely, for example, can use 30～300 ℃ temperature, and more preferred 50～250 ℃, preferred especially 100～200 ℃.When temperature of reaction is hanged down, for the reaction times that reaches abundant reaction prolongs, when temperature of reaction is high, the processing transfiguration that the is shaped difficulty that is easy to get.

Reaction can be carried out at a certain temperature, also can be optionally, and multistage or transformation temperature continuously.In addition, also can there be multiple setting in the reaction times, for example, can carry out Procuring under 60 ℃/1～10 minute, again the method that was cured under 100 ℃/1～60 minute.

Pressure during reaction also can optionally have multiple setting, also can react under normal pressure, high pressure or decompression state.

Then, the material that can make an addition to solidification compound of the present invention and light-shielding paste is introduced.

In solidification compound of the present invention and light-shielding paste,, can add various thermosetting resins for reaching purposes such as improving characteristic.As thermosetting resin, can give an example out, Resins, epoxy, cyanate ester resin, resol, polyimide resin, urethane resin, bimaleimide resin etc., but be not limited to these.Wherein, from the viewpoint of practical excellents such as cementability, preferred epoxy.

As Resins, epoxy, can enumerate, for example, with phenolic varnish phenol type Resins, epoxy, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin, the Bisphenol F diglycidylether, bisphenol A diglycidyl ether, 2,2 '-two (4-glycidoxypropyl cyclohexyl) propane, 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, the vinyl cyclohexene dioxide, 2-(3, the 4-epoxycyclohexyl)-5,5-spiral shell-(3, the 4-epoxy cyclohexane)-1, the 3-diox, two (3, the 4-epoxycyclohexyl) adipic acid ester, 1,2-cyclopropane dicarboxylic acid bisglycidyl ester, isocyanuric acid three-glycidyl ester, monoene propyl group Diglycidylisocyanury-ester, Resins, epoxy such as single glycidyl diallyl chlorinated isocyanurates are used hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, the trialkyl Tetra Hydro Phthalic Anhydride, aliphatic anhydride such as hydrogenation methyl carbic anhydride are solidified the material that obtains.These Resins, epoxy or solidifying agent can use separately also respectively and can a plurality ofly be used in combination.

These thermosetting resins can use separately, also can a plurality ofly be used in combination.

Addition as heat-curing resin has no particular limits.Following 5 whole weight % of solidification compound, the more preferred 10 weight % of being limited to of preferred usage quantity; Be limited to 50 weight % in the solidification compound on the preferred usage quantity, more preferred 30 weight %.If addition is few, being difficult to obtain with cementability etc. is the effect of purpose, if addition is many, then becomes fragile easily.

The substance dissolves that thermosetting resin can obtain resin raw material and/or curing is in (A) composition and/or (B) composition, becoming uniform state mixes, also can pulverize the back and mix, can also be dissolved in solvent and mix etc. and to become dispersion state with particle state.On the cured article that obtains is easy to more evenly this point, be preferably dissolved in (A) composition and/or (B) composition, become uniform state and mix.At this moment, thermosetting resin directly can be dissolved in (A) composition and/or (B) in the composition, also can be with uniform mixing such as solvents, can also remove to desolvate after this become uniform dispersion state and/or admixture.

Disperse heat-curing resin and when using, its median size can be done various settings, the lower limit of preferred median size is 10nm, and the upper limit of preferred median size is 10 μ m.The distribution of particle system also can be arranged, it can be single dispersion, also can be particle diameter with a plurality of peak values, the better viewpoint but, coating low from the viscosity of solidification compound and light-shielding paste becomes easily, the coefficient of variation of preferable particle size is below 10% or 10%.

In solidification compound of the present invention and light-shielding paste,, can add various thermoplastic resins for reaching the purpose of improving characteristic etc.Can use various resins as thermoplastic resin.For example, can give an example out, butyl polyacrylate resinoids such as monomeric random, block of the homopolymer of polymethylmethacrylate resinoids (for example Hitachi changes into the system ォプトレッ of society Star etc.) such as monomeric random, block of the homopolymer of methyl methacrylate or methyl methacrylate and other or graftomer, butyl acrylate or butyl acrylate and other or graftomer etc. are the acrylic resin of representative; Contain with dihydroxyphenyl propane, 3,3,5-trimethylammonium cyclohexylidene bis-phenol etc. are as the polycarbonate resins such as polycarbonate resin (for example Supreme Being people society makes APEC etc.) of monomer structure; The resin that homopolymerization such as norbornene derivative, vinyl monomer or copolymerization obtain, norbornene derivative is carried out the resin that ring-opening metathesis polymerization obtains, or cycloolefin resinoid such as its hydride (for example, Mitsui Chemicals society system APEL, Japanese ゼォ Application society system ZEONOR, ZEONEX, the system ARTON of JSR society etc.); Alkene such as the multipolymer of ethene and maleinamide-maleinamide resinoid (for example eastern ソ system TI-PAS of one society etc.); Glycolss such as bisphenols of dihydroxyphenyl propane, two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes etc. or glycol ether, the polyester resins such as polyester (for example bell spins the system O-PET of society etc.) that form with phthalic acid class such as terephthalic acid, m-phthalic acid or the polycondensation of aliphatic dicarboxylic acid class; Polyethersulfone resin; Polyarylate resin; Polyvinyl acetal resin; Polyvinyl resin; Acrylic resin; Polystyrene resin; Polyamide resin; Silicone resin; Beyond the fluoro-resin etc., also have rubber-like resins such as natural rubber, EPDM etc., still, be not limited to these.

As thermoplastic resin, also can contain in the molecule with SiH and have reactive carbon-to-carbon double bond and/or contain the SiH group.On the cured article that obtains becomes stronger and more unyielding this point easily, contain with the SiH group in the preferred molecule and have the SiH group that on average contains in reactive carbon-to-carbon double bond and/or 1 molecule more than 1 or 1.

As thermoplastic resin, also can have other crosslinked group.As the crosslinkable groups of this moment, can enumerate epoxy group(ing), amino, free-radical polymerised unsaturated group, carboxyl, isocyanate group, hydroxyl, alkoxysilyl etc.On the viewpoint that the thermotolerance of the cured article that obtains uprises easily, on average contain crosslinkable groups in preferred 1 molecule more than 1 or 1.

Molecular weight as thermoplastic resin, there is no particular limitation, but from (A) composition or (B) intermiscibility of composition improve easily on this point, preferred number average molecular weight is below 10000 or 10000, opposite from being more preferably below 5000 or 5000, from the cured article that the obtains stronger and more unyielding this point that becomes easily, more than the number-average molecular weight preferred 10000 or 10000, be more preferably more than 100000 or 100000.Also there is no particular limitation about the distribution of molecular weight, but from the viscosity of mixture reduce, plasticity becomes on the better this point easily, preferred molecular weight is distributed as below 3 or 3, below more preferred 2 or 2, below preferred especially 1.5 or 1.5.

Can use single material as thermoplastic resin, also can a plurality ofly be used in combination.

Addition as thermoplastic resin has no particular limits.Following 5 whole weight % of solidification compound, the more preferred 10 weight % of being limited to of preferred usage quantity; Be limited to 50 whole weight % of solidification compound, more preferred 30 weight % on the preferred usage quantity.If addition is less than 5 weight %, the cured article that obtains has the tendency that is easy to become fragile, if addition, then has the tendency of thermotolerance (Young's modulus under the high temperature) step-down greater than 50 weight %.

Thermoplastic resin can be dissolved in (A) composition and/or (B) composition, becomes uniform state and mixes, and also can pulverize the back and mix with particle state, can also be dissolved in solvent and mix etc. as dispersion state.On the cured article that obtains is easy to more evenly this point, be preferably dissolved in (A) composition and/or (B) composition, become uniform state and mix.At this moment, thermoplastic resin directly can be dissolved in (A) composition and/or (B) in the composition, also can also remove after this and desolvate with uniform mixing such as solvents as the dispersion state and/or the admixture of homogeneous.

Disperse thermoplastic resin and when using, its median size can be done all settings, the lower limit of preferred median size is 10nm, and the upper limit of preferred median size is 10 μ m.The distribution of particle system also can be arranged, and can be single dispersion, also can be the particle diameter with a plurality of peak values, but the viewpoint low from the viscosity that makes solidification compound easily, that plasticity is good, the coefficient of variation of preferable particle size is below 10% or 10%.

In addition, in solidification compound of the present invention and light-shielding paste, can add filler.

Can use various materials as filler, can enumerate, for example, headed by mineral fillers such as silver powder, glass fibre, carbon fiber, carbon black, graphite, talcum, and usually use and/or the filler that proposes etc. as the filler of the sealing material in the past of epoxies etc.

In addition, can be to the light-shielding paste that comprises thermoplastic resin and inorganic materials, comprise and add for example silica-based fillers such as quartz, thermal silica, settleability silicon-dioxide, anhydrous silicic acid, fused silica, crystallinity silicon-dioxide, ultra-fine soft silica in the light-shielding paste of thermosetting resin and inorganic materials.This silica-based filler reduces linear expansivity outstanding effect viewpoint from being difficult for hindering curing reaction, is preferred.

Filler can be done suitable surface treatment.As surface treatment, the same method that can enumerate Yu in above-mentioned inorganic materials, enumerate.

In addition, can also enumerate the method for adding filler.Can enumerate, for example, alkoxide, hydrochlorate and the halogenide etc. of metals such as water-disintegrable silane monomer such as organoalkoxysilane, acyloxy silane, halogenated silane or oligopolymer, titanium, aluminium are added in solidification compound of the present invention and the light-shielding paste, in solidification compound and light-shielding paste or in the partial reaction thing of solidification compound and light-shielding paste, react, thereby in solidification compound and light-shielding paste, generate the method for filler.

As the median size of filler, on the good this point of impregnability, preferred 10 μ m or below the 10 μ m are more preferably 5 μ m or below the 5 μ m.

Ratio as packing material particle diameter 50 μ m or the particle more than the 50 μ m is easy on the good this point in impregnability, and preferred 1 weight % or below the 1 weight % is more preferably 0.1 weight % or below the 0.1 weight %.

About the size distribution of filler, headed by the material that uses as the filler of sealing materials in the past such as epoxies and/or propose, can do various settings.For example, can be set at the above particle of 24 μ m or 24 μ m and be 15 weight % or more than the 15 weight %, and 1 μ m or the following particle of 1 μ m are 3 weight % or more than the 3 weight %.

The ratio of the particle that the median size of filler, the particle diameter of filler 50 μ m or 50 μ m are above can use the little footpath of laser method particle-size analyzer to measure.

For the specific surface area of filler, headed by the material that uses as the filler of sealing materials in the past such as epoxies and/or propose, can do various settings.For example, can be set at 4m arbitrarily ²/ g or 4m ²More than/the g, 4m ²/ g or 4m ²Below/the g, 10m ²/ g or 10m ²/ g is with inferior.

Specific surface area can be measured by the attached specific area measuring device of BET method single suction.

For the vitrifying rate of filler, headed by the material that uses as the filler of sealing materials in the past such as epoxies and/or propose, can do various settings.For example, can be set at 97% or 97% arbitrarily with first-class.

As the shape of filler, from the viewpoint of the viscosity that is easy to make sealing material, preferred globular filler.

Filler can use separately, also can use simultaneously more than 2 kinds or 2 kinds.

There is no particular limitation for the addition of filler, but obviously and the viewpoint of the good fluidity of composition from the effect that reduces linear expansivity, the lower limit of preferred addition is 30 weight % in whole compositions, more preferred 50 weight %, the upper limit of preferred addition is 80 weight % in whole compositions, more preferred 70 weight %.

As the blending means of filler, can adopt the whole bag of tricks.But on the storage stability of the intermediate raw material of solidification compound and light-shielding paste was easy to become good this point, the mixture that preferably will mix (C) composition and filler in (A) composition became the phase-splitting blending means with (B).Adopt when being oriented in the method for mixing (A) composition in the mixture that has mixed (C) composition and/or filler in (B) composition, in the presence of (C) composition and/or not, because (B) moisture and/or the filler in composition and the environment has reactivity, therefore produce rotten in the medium meeting of storage.

Also can in solidification compound of the present invention and light-shielding paste, add anti-aging agent.Can enumerate normally used anti-aging agent as anti-aging agent, for example, citric acid or phosphoric acid, sulphur class anti-aging agent etc.As sulphur class anti-aging agent, can enumerate, thio-alcohol, mercaptan salt, carbothioic acid ester class, contain sulfide-based sulfide-based, the multiple sulfides of Hinered phenols, dithionic acid salt, Thiourea, thiophosphoric acid salt, sulfonium compound, thioaldehydes class, thioketones class, thioacetal class, mereaptol class, single sulfo-acids, polythio acids, thioamide analog, sulfoxide class etc.In addition, these anti-aging agent can use separately, also can use simultaneously more than 2 kinds or 2 kinds.

Can in solidification compound of the present invention and light-shielding paste, add free radical inhibitors.As free radical inhibitors, can enumerate, for example, 2,6-di-tert-butyl-4-methy phenol (BHT), 2, the phenols free radical inhibitors of 2 '-methylene radical-two (4-methyl-6-tert butyl phenol), four (methylene radical-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionic ester) methane etc. or Phenyl beta naphthylamine, alpha-naphthylamine, N, N '-secondary-butyl-p-phenylenediamine, thiodiphenylamine, N, N '-diphenyl-para-phenylene diamine waits amine free radical inhibitors etc.In addition, these free radical inhibitors can use separately, also can use simultaneously more than 2 kinds or 2 kinds.

Also can in solidification compound of the present invention and light-shielding paste, add UV light absorber.As UV light absorber, can enumerate for example 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, two (2,2,6,6-tetramethyl--4-piperidyl) sebate etc.In addition, these UV light absorber can be used separately, also can use simultaneously more than 2 kinds or 2 kinds.

In the scope of not damaging purpose of the present invention and effect, can be in solidification compound of the present invention and light-shielding paste, interpolation use as the filler of sealing materials in the past such as epoxies and/or the material that proposes headed by, and tinting material, releasing agent, fire retardant, flame retardant, tensio-active agent, defoamer, emulsifying agent, flow agent, anticrater agent, ion capturing agent, the thixotropy imparting agent, or tackifiers, preserve the stable modification agent, antiozonidate, photostabilizer, tackifier, softening agent, reactive diluent, oxidation inhibitor, thermo-stabilizer, the electroconductibility imparting agent, static inhibitor, radioactive rays blocking agent, nucleator, Phosphorus peroxide decomposer, lubricant, pigment, metal passivator, the thermal conductivity imparting agent, rerum natura is adjusted agent etc.

Solidification compound of the present invention and light-shielding paste also can be dissolved in the solvent and use.There is no particular limitation for operable solvent, if enumerate particularly, can suitably use varsols such as benzene, toluene, hexane, heptane; Tetrahydrofuran (THF), 1,4-diox, 1, ether solvents such as 3-two oxa-s penta ring, ether; Ketones solvents such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK); Chloroform, methylene dichloride, 1, halogen solvents such as 2-ethylene dichloride.As solvent, preferred toluene, tetrahydrofuran (THF), 1,3-two oxa-s penta ring, chloroform.

The quantity of solvent of using can suitably be set, but is 0.1mL with respect to the lower limit of the preferred usage quantity of 1g solidification compound that uses and light-shielding paste, and the upper limit of preferred usage quantity is 10mL.If usage quantity, then has the tendency of the effect of the solvent that is difficult to obtain to use lowering viscousity etc. less than 0.1mL, in addition, if usage quantity greater than 10mL, then has solvent residual in material, problems such as thermal destruction take place easily, and the tendency that is unfavorable for cost is arranged.

These solvents can use separately, also can mix use more than 2 kinds or 2 kinds.

[using the LED shell and the photodiode of light-shielding paste of the present invention]

Photodiode as semiconductor device of the present invention, be to have to possess the peristome that comprises bottom surface and sidewall and in the peristome bottom surface, each end of positive outer electrode and the outer electrode of bearing, the LED shell that obtains with the shaping resin monolithic molding according to the interval of separating regulation with exposing, with the luminous element that on the bottom surface of LED, is provided with shell, and by in fact only being coated with light-shielding paste of the present invention with the sidewall of shell, and/or its light-shielding resin that obtains after solidifying and shading at this LED.

" in fact only at sidewall " though the meaning be that light-shielding paste of the present invention flows out near the bottom surface the sidewall and when solidifying, only otherwise give as the performance of the photodiode of the present invention of the finished product and bring baneful influence, just comprise this situation.

In addition, as semiconductor device of the present invention, can enumerate the device that the LED around luminous element makes with the bottom surface of shell and sidewall formation light-shielding resin and shading.At this moment, " luminous element around LED with the bottom surface and the sidewall of shell " be meant bottom surface and the part that in sidewall, does not contact with luminous element at LED usefulness shell.

In addition, in the past, since the operation thermal history of assembled semiconductor device, shell resin generation thermo-color, and reflectivity reduces.Therefore, luminous efficiency reduces, and causes low output rating.In addition,, will reduce the light that luminous element sends, cause low output rating if light-shielding resin contacts with luminous element.But, in the present invention, the light-shielding resin that comprises the resin of excellent heat resistance by use, by in fact only using the sidewall of shell at LED, or in the bottom surface and sidewall the light-shielding resin layer is not set in contact with luminous element, can prevent can provide the semiconductor device with high optical output power because the reflectivity that the assembling procedure thermal history causes reduces.

In addition, LED of the present invention with the feature of shell is, in fact only has light-shielding resin at LED with the sidewall of shell peristome.

Shell before the coating light-shielding paste can use various materials to make, can enumerate, for example resins such as polycarbonate resin, polyphenylene sulfide, Resins, epoxy, acrylic resin, polyorganosiloxane resin, ABS resin, polybutylene terephthalate resin, polyphthalamide resin, Resins, epoxy, BT resin, liquid crystalline polymers.From stable on heating viewpoint, preferred semicrystalline polymeric resin, polyphthalamide resin, BT resin, liquid crystalline polymers.From the viewpoint of cementability, preferably as polyphthalamide resin, the polybutylene terephthalate resin of semicrystalline polymeric resin.

In addition, also can use the shell of pottery system.

The peristome of shell can be different shapes such as rectangle, circle, ellipse.

As the coating process of light-shielding paste, can use print process as common known liquid resin coating process, cladding process, transfer printing etc.For example, can be coated with by impact molding, ink-jet printing process, pickling process, woodburytype, porous printing, screen painting or mask.In addition, can use pin scraper hairbrush etc. to be coated with.

Be used in the luminous element of photodiode of the present invention, there is no particular limitation, can use the employed luminous element of known in the past photodiode.As such luminous element, can enumerate, by for example the whole bag of tricks of mocvd method, HDVPE method, liquid-phase growth method, optionally, and on the substrate of the buffer layer that is provided with GaN, AlN etc., the element that the laminated semiconductor material is made.Substrate as this moment can use various materials, can enumerate, for example sapphire, spinel, SiC, Si, ZnO, GaN single crystal etc.Wherein, from the good costly viewpoint of GaN, industrial utilization of easy formation crystallinity, preferably use sapphire.

As the semiconductor material of lamination, can enumerate GaAs, GaP, GaAlAs, GaAsP, AlGaInP, GaN, InN, AlN, InGaN, InGaAlN, SiC etc.Wherein, from obtaining the viewpoint of high brightness, preferred nitride compounds semi-conductor (In _xGa _yAl _zN).In such material, also can contain activator etc.

As the structure of luminous element, can enumerate, have the homogeneity combination that MIS engages, pn engages, PIN engages, heterogeneous combination or double heterojunction and close structure etc.In addition, also can make single or multiple quantum well structure.

Luminous element can be provided with passivation layer, also can not be provided with.

Luminous element can pass through known in the past method and form electrode.

Electrode on the luminous element can in all sorts of ways and lead terminal etc. is electrically connected.As electric connecting part, preferably be connected etc. goodly with the resistive mechanical electric of the electrode of luminous element, can enumerate, for example, use the bonding wire of gold and silver, copper, platinum, aluminium or their alloy.In addition, also can use the conductive adhesive of in resin, having filled electroconductive stuffings such as silver, carbon.Wherein, from the good viewpoint of operability, preferably use aluminum steel or gold thread.

Make luminous element according to the method described above, in photodiode of the present invention, the luminous intensity of luminous element so long as the luminous intensity of vertical direction at 1cd or more than the 1cd, can use photodiode arbitrarily, but the luminous intensity by using vertical direction is during as 2cd or the luminous element more than the 2cd, effect of the present invention is remarkable, and when using the luminous element more than 3cd or the 3cd, effect of the present invention is more remarkable.

Luminous output rating as luminous element has no particular limits, can use any power, but when 20mA, effect of the present invention is remarkable when using the luminous element more than 1mW or the 1mW, when 20mA, effect of the present invention is more remarkable when using the luminous element more than 4mW or the 4mW, when 20mA, and particular significant effect of the present invention when using the luminous element more than 5mW or the 5mW.

The emission wavelength of luminous element can use the various wavelength from the ultra-violet region to the infrared spectral range, but when using the main glow peak wavelength as 550nm or the luminous element below the 550nm, effect of the present invention is remarkable.

The luminous element that uses can be same kind bill coloured light, also can use a plurality of bill looks or polychromatic light.

As the employed lead terminal of photodiode of the present invention, preferably good with adaptation, the electroconductibility of electric connecting parts such as bonding wire, as the preferred 300 μ Ω cm of the resistance of lead terminal or below the 300 μ Ω cm, more preferred 3 μ Ω cm or below the 3 μ Ω cm.For example can enumerate as these lead terminal materials, iron, copper, ferruginous copper, stanniferous copper, and the material that obtains such as silver-plated on these materials, nickel etc.These lead terminals are the dispersion that obtains good light, also can suitably adjust glossiness.

Photodiode of the present invention can be by being made by various resin-coated luminous elements, and still, said in this case coating is not limited to directly seal above-mentioned luminous element, also comprises the situation of indirect coating.Can use Resins, epoxy, polyorganosiloxane resin, acrylic resin, urea-formaldehyde resin, imide resin etc. as sealing resin.In addition, also can use the glass capsulation luminous element.

Method as sealing also can make and ins all sorts of ways.For example, can fluid composition be injected into the light cup that is provided with luminous element in the bottom, recess, shell recess etc. by the method beyond the blender loader, by curing such as heating, also can it be flowed the composition heating of solid state or high viscosity liquid etc., similarly inject reheat such as shell sunk part etc. and be cured.

The shape of covered section also has no particular limits, and can adopt different shape.Can enumerate, for example, lensing, tabular, film like, spy open shape that flat 6-244458 communique puts down in writing etc.These shapes can form by the shaping curing composition, also can curing composition after, form by following process.

In addition, photodiode of the present invention goes for known in the past variety of way.Can enumerate, for example, the mode of the layer of reflected light or optically focused is set at the luminous element back side, form the mode of the painted portion of complementary color in the bottom corresponding to the flavescence of sealing resin, the mode of the film of the short light of specific absorption main glow peak wavelength is set on luminous element, behind soft or aqueous sealing material sealed light emitting element, mode with mechanically resistant material moulding on every side, with containing the light that absorption is sent from luminous element, after sending the material seal luminous element of fluor of the longer fluorescence of wavelength, mode with moulding on every side, the mode that material is shaped afterwards in advance and luminous element formalizes simultaneously that contains fluor, opening flat 6-244458 communique as the spy puts down in writing, molding material is made the mode that special shape improves luminous efficiency, shell is made the mode of the sunk part of 2 sections shapes for reducing brightness disproportionation, photodiode is inserted through hole fixed mode, form the mode of film of the light of the short wavelength of specific absorption main light emission wavelength on luminous element surface, flip-chip connection by having used scolding tin projection etc. etc., luminous element and wire terminal part etc. are connected, thereby derive the mode etc. of light from orientation substrate.

Photodiode of the present invention can be used in known in the past various uses.Particularly, can enumerate, for example retreat light source, indicating meter, decoration, various light fixtures of lamp, illumination, sensing light source, auto meter light source, signal lamp, pilot lamp, display equipment, planar twinkler etc.

＜second of the present invention

Below, the formation method of light-shielding resin layer of the present invention is described.

Has the peristome that comprises bottom surface and sidewall and in the peristome bottom surface, each end of positive outer electrode and the outer electrode of bearing, the LED that obtains with the shaping resin monolithic molding according to the interval of separating regulation with exposing with shell, only on sidewall, form the method for light-shielding resin layer, can roughly be divided into following 3 stages.

(1) light-shielding paste is coated on operation on the body material

(2) the driving fit LED operation of the peristome of shell

(3) operation that LED is heated with the state that makes progress with the peristome of shell

Below, be divided into each operation and describe.

(1) light-shielding paste is coated on operation on the body material

Light-shielding paste can be coated on the body material by various known methods.The material of body material can be used for example various materials such as resin system, rubber system, glass, pottery system, metal system.The shape of body material can be used for example curved surface shape body materials such as plane body material, cylinder, ball such as flat board, leveling board, tabular band, Δ shape cylinder.

To body material coating light-shielding paste can use teeming practice, cladding process, use T pattern extrusion molding, filling with the whole bag of tricks such as method that flood in the bath of light-shielding paste.In addition, can use various liners (スペ one サ one) for the purpose that reaches the control thickness.Preferred 0.1 second～24 hours of the time of coating, be more preferably 1 second～1 hour, preferred especially 1 minute～30 minutes.Preferred 5 ℃～100 ℃ of the temperature of coating is more preferably 10 ℃～50 ℃, preferred especially 15 ℃～30 ℃.Coating in a vacuum, in the air and nitrogen, argon etc. can suitably not implement in the arbitrary gas environment in the reactive gas.Process furnace can use various process furnace such as recirculation furnace, infrared heating oven.In addition, for reaching the purpose that prevents to sneak into foreign matter, preferably in dust free chamber, carry out.

(2) the driving fit LED operation of the peristome of shell

On the body material that has been coated with (a 1) light-shielding paste that forms, driving fit LED adheres to light-shielding paste with the peristome of shell on the top of peristome.The body material of coating light-shielding paste is when being plane, carries out with deadweight or the compacting by pressurizeing, the whole bag of tricks such as compacting by cylinder that the driving fit of the peristome of shell can be by shell with LED.In addition, the body material that has been coated with light-shielding paste is the curved surface shape, for example during the cylinder shape, by rotating this cylinder to peristome, in addition by LED with the peristome of shell and the cylinder that has been coated with light-shielding paste closely by in the middle of the cylinder, adhere to light-shielding paste at LED with the peristome top of shell.

Preferred 0.01 second～24 hours of the time of driving fit was more preferably 0.1 second～1 hour, preferred especially 1 second～5 minutes.Preferred 5 ℃～100 ℃ of the temperature of driving fit is more preferably 10 ℃～50 ℃, preferred especially 15 ℃～30 ℃.Can control the light-shielding paste adhesion amount by the temperature-time of driving fit.Driving fit in a vacuum, in the air and nitrogen, argon etc. can suitably not implement in the arbitrary gas environment in the reactive gas.Process furnace can use various process furnace such as recirculation furnace, infrared heating oven.In addition, for reaching the purpose that prevents to sneak into foreign matter, preferably in dust free chamber, carry out.

(3) operation that heats of the state that makes progress with the peristome of shell with LED

Then, heat with the state that makes progress with the peristome of shell,, can make the sidewall curtain coating of only using shell in (2) item attached to the light-shielding paste on shell peristome top at LED by control heat-up time/temperature with LED.The meaning of said in this specification sheets " state that makes progress with the peristome of shell with LED " be with LED with the bottom electrode of shell towards last, and this bottom electrical pole-face placed state for the vertical position of plummet.

Vertical precision only otherwise bring very big fault can for the operation of (3) of the present invention, can roughly allow ± 10 degree.Heating temperature can suitably be set according to the adhesion amount of light-shielding paste, viscosity, thixotropy etc.For preventing the shell deterioration, preferred 30 ℃～200 ℃, be more preferably 40 ℃～100 ℃, preferred especially 50 ℃～80 ℃.Can suitably set heat-up time according to the adhesion amount of light-shielding paste, viscosity, thixotropy etc.From the viewpoint of productivity, preferred below 1 hour or 1 hour, be more preferably below 30 minutes or 30 minutes, preferred especially below 15 minutes or 15 minutes.Heating in a vacuum, in the air and nitrogen, argon etc. can suitably not implement in the arbitrary gas environment in the reactive gas.Process furnace can use various process furnace such as recirculation furnace, infrared heating oven.In addition, heating can stage be carried out.For example, can be 60 ℃ of heating 30 minutes down, 80 ℃ of heating 30 minutes down, 100 ℃ of heating interim heating in ground in 30 fens down.

Below, the light-shielding paste that can use in the formation method of light-shielding resin layer of the present invention is described.

As this light-shielding paste, can suitably use above-mentioned light-shielding paste, comprise the light-shielding paste of above-mentioned solidification compound etc.

This light-shielding paste can use various viscosity.For guaranteeing good coating, preferably at the viscosity height of normal temperature (23 ℃), and the viscosity of (30 ℃) is low during heating.Under normal temperature (23 ℃), more than preferred 10 pools or 10 are moored, more than (30 ℃) preferred 1 pool or 1 is moored during heating.Viscosity can be measured with E type rotational viscosimeter.

If the thixotropy of this light-shielding paste is big, then flowability becomes bad, just can not reach purpose of the present invention.Therefore, preferred 0.8～1.2 in 23 ℃ thixotropy (viscosity ratio), be more preferably 0.9～1.1, preferred especially 0.95～1.05.Thixotropy (viscosity ratio) can use E type rotational viscosimeter to measure, and the rotation number of viscometer can be decided to be the value of 10rpm/1rpm usually, but also can adopt various combined values such as 20rpm/2rpm, 50rpm/5rpm, 5rpm/0.5rpm.

If the solidified nature of this light-shielding paste is big, in the operation that the state that makes progress with the peristome of shell with LED in (3) heats, light-shielding paste can solidify before all at curtain coating full packages shell-side face, can not obtain good light shield layer.Therefore preferred 15 seconds～90 seconds of set time under 115 ℃, be more preferably 20 seconds～75 seconds, preferred especially 30 seconds～60 seconds.Can estimate set time by the gelation time that is called as the locking key adjusting time.Measuring method is as follows.By being pressed on the hot-plate (115 ℃ ± 3 ℃), stopwatch picks up counting simultaneously with the about 50mg of light-shielding paste.Have again, smear, no longer show time of fluidity as set time up to light-shielding paste with scraper.

If this light-shielding paste is mobile big, then in the operation that (2) driving fit LED makes progress LED with the operation of the peristome of shell and/or (3) with the peristome of shell state heats, the electrode part of bottom surface can take place to be cast to from the side of shell, makes the fault that led chip can not conducting.Therefore, preferred light-shielding paste has suitable flowability.On the other hand, in fact only otherwise take place aforesaid can not conducting etc. fault, also no problem even a part flow to the bottom surface after fixing.

The mobile method that can be used in this light-shielding paste of curtain coating on the sheet glass is estimated.This method as shown below.After being coated on the sheet glass with the round shape of 8mm diameter the light-shielding paste of about 50mg,, be determined at about 21 ℃ of distances that flow down when keeping 10 minutes down with this sheet glass about 80 degree and fixing that tilt.Preferred 5mm～the 30mm of the distance that flows down is more preferably 5～20mm, preferred especially 5～15mm.In addition, at about 60 ℃ of preferred 10mm～70mm of distance that flow down when keeping 5 minutes down, be more preferably 10～40mm, preferred especially 10～30mm.Heating can be used recirculation furnace.

In addition, above-mentioned light-shielding paste being solidified resulting light-shielding resin describes.

This light-shielding resin requires to have the thermotolerance of tolerance solder reflows (solder reflow) etc.When thermotolerance is hanged down, will be painted when solder reflows, become the reason that LED brightness descends.Therefore, the light-shielding resin by this light-shielding paste manufacturing preferably has high heat resistance.Thermotolerance can heat 3 minutes down at 260 ℃ by light-shielding paste being coated with into the formed light-shielding resin of substrate shape, and the yellow chromaticity of evaluation light-shielding resin (YI) estimate by yellowness index.As 100 o'clock, the value of heating after 3 minutes was preferred 100～150 down at 260 ℃, is more preferably 100～140, preferred especially 100～130 with the initial value of yellow chromaticity.Yellow chromaticity can use colour-difference meter to measure.

This light-shielding resin requires to have the photostabilization of the light that sends from led chip for reflection.If photostabilization is low, then can be painted, become the reason that LED brightness descends.Therefore, the light-shielding resin by this light-shielding paste manufacturing preferably has high-light-fastness.Photostabilization can be carried out rayed on the formed light-shielding resin of substrate shape and estimates by being coated with at light-shielding paste.Fast light test uses the super xenon lamp type Weatherometer (super xenon weathermeter) of Suga trier manufacturing at radiant flux density 0.18kW/m ², Continuous irradiation 1 hour 42 minutes, the round-robin test of rainfall in 18 minutes 63 ℃ of blackboard thermoscope temperature, under the test conditions of humidity 50%, was carried out 330 hours.The yellow chromaticity initial value is decided to be at 100 o'clock, is 100～150 by the value behind the light fastness test of xenon lamp type Weatherometer preferably, more preferred 100～140, preferred especially 100～130.Yellow chromaticity can use colour-difference meter to measure.

This light-shielding resin is preferably the opacifying property of guaranteeing necessity and has suitable thickness.Preferred 1～1000 μ m of thickness is more preferably 5～500 μ m, preferred especially 50～100 μ m.Thickness can be measured by the non-destructive inspection that uses ultrasonic microscope, roentgenoscope etc.In addition, make section, can pass through scanning electron microscope (SEM) and measure according to state with light-shielding resin and real estate.

This light-shielding resin is that the reliability of guaranteeing LED must have the high adhesion with shell.If cementability is low, shell and moulded piece resin can be peeled off, and become the reason that LED does not work.Cementability can be estimated by carry out mould shearing (die shear) test on the substrate that forms the light-shielding resin layer.The mould shear testing maschine can use for example bonding test machine 2400 of universal type of デイジ society manufacturing.Fast light test uses the super xenon lamp type Weatherometer of Suga trier manufacturing at radiant flux density 0.18kW/m ², Continuous irradiation 1 hour 42 minutes, the round-robin test of rainfall in 18 minutes 63 ℃ of blackboard thermoscope temperature, under the test conditions of humidity 50%, was carried out 330 hours.The bonding strength initial value is decided to be at 100 o'clock, is more than 70 or 70 by the value behind the light fastness test of xenon lamp type Weatherometer preferably, more than more preferred 80 or 80, more than preferred especially 90 or 90.

Employed light-shielding paste, light-shielding resin also go for LED shell and photodiode in the formation method of light-shielding resin of the present invention.In addition, the explanation of LED usefulness shell and photodiode as previously mentioned.

The optimum regime that carries out an invention

Below, embodiments of the invention and comparative example are shown, but the present invention is not limited to these.

(synthesis example 1)

As the triallyl isocyanurate and 1,3,5 of (B) composition, the reactant of 7-tetramethyl-ring tetrasiloxane synthetic

In the separated type flask of 5L, add toluene 1.8kg, 1,3,5,7-tetramethyl-ring tetrasiloxane 1.44kg, heating makes internal temperature reach 104 ℃.To xylene solution (platinum that the contains 3wt%) 1.44mL of the triallyl isocyanurate 200g that wherein drips, platinum vinylsiloxane coordination compound, the mixture of toluene 200g.Reflux is 7 hours in 120 ℃ oil bath.Add 1-ethynyl-1-hexalin 1.7g.Decompression is heated up in a steamer unreacted 1,3,5,7-tetramethyl-ring tetrasiloxane and toluene.Learn that by 1H-NMR this material is 1,3,5, the material that the part of the SiH base of 7-tetramethyl-ring tetrasiloxane and triallyl isocyanurate reaction obtain (is called partial reaction thing B1, SiH value: 8.2mmol/g, allyl base value: 0.12mmol/g).Resultant is a mixture, but the compound that contains the following structure with (B) of the present invention composition is as main component.In addition, contain platinum vinylsiloxane coordination compound as (C) of the present invention composition.

(embodiment 1)

The mixture that uses triallyl isocyanurate 54.51g and diallyl list glycidyl chlorinated isocyanurates 87.03g is as (A) composition, the reactant of synthesis example 1 (B1) 162.64g is as (B) composition, as (D) composition, trimethyl borate 1.52g is as (E) composition as (C) composition, γ-glycidoxypropyltrime,hoxysilane 7.60g for the xylene solution of platinum vinylsiloxane coordination compound (platinum that contains 3wt%) 913mg.With above-mentioned (A) composition, (C) composition and (E) composition be pre-mixed stirring, make mixture A liquid.In addition, above-mentioned (B) composition, (D) composition and 1-ethynyl-1-hexalin 90mg is pre-mixed stirring, makes mixture B liquid.Mix said mixture A liquid and mixture B liquid and stir deaeration and become single-component mixture.In this mixture 2.5g, mix titanium oxide (the former industry of stone (strain), イペ one Network R-820) 2.5g, stir deaeration and obtain light-shielding paste as (F) composition.

(embodiment 2)

In the single-component mixture 2.5g of (A)～(E) composition that embodiment 1 obtains, mix titanium oxide (the former industry of stone (strain) as (F) composition, イペ one Network R-820) 2.5g, remix silicon-dioxide (Japanese ァェロジ Le (strain), ァェロジ Le 300) 75mg stirs deaeration and obtains light-shielding paste.

(embodiment 3)

Use triallyl cyanurate 12.04g as (A) composition, the reactant of synthesis example 1 (B1) 17.96g is as (B) composition, as (D) composition, trimethyl borate 150mg is as (E) composition as (C) composition, γ-glycidoxypropyltrime,hoxysilane 750mg for the xylene solution of platinum vinylsiloxane coordination compound (platinum that contains 3wt%) 90mg.With above-mentioned (A) composition, (C) composition and (E) composition be pre-mixed stirring, make mixture A liquid.In addition, above-mentioned (B) composition, (D) composition and 1-ethynyl-1-hexalin 90mg is pre-mixed stirring, makes mixture B liquid.Mix said mixture A liquid and mixture B liquid and stir deaeration and become equal mixture.Mix titanium oxide (the former industry of stone (strain), the イペ one Network R-820) 2.5g as (F) composition in this mixture 2.5g, remix silicon-dioxide (Japanese アェロジ Le (strain), ァェロジ Le 300) 125mg also stirs deaeration and obtains light-shielding paste.

(embodiment 4)

The light-shielding paste that embodiment 1～3 is obtained is coated on the polyphthalamide resin molding, controls thickness with adhesive tape as liner, solidifies down at 100 ℃ and forms light shield layer in 1 hour.Thereon by according to the bonding mould shearing test of the caking agent of following method manufacturing mould.

Bond layer after the heating, was solidified to form under 150 ℃/1 hour, 180 ℃/30 minutes the condition at 60 ℃/6 hours, 70 ℃/1 hour, 80 ℃/1 hour, 120 ℃/1 hour.

(comparative example 1)

On the polyphthalamide resin molding, by according to the bonding mould shearing test of the caking agent of following method manufacturing mould.

The making of＜caking agent composition 〉

With triallyl isocyanurate 12.04g, the xylene solution of platinum vinylsiloxane coordination compound (platinum that contains 3wt%) 90mg and trimethyl borate 150mg are pre-mixed stirring, make mixture A liquid.In addition, reactant (B1) 17.96g, γ-glycidoxypropyltrime,hoxysilane 750mg and the 1-ethynyl-1-hexalin 90mg with synthesis example 1 is pre-mixed stirring, making mixture B liquid.Mixing said mixture A liquid and mixture B liquid also stirs deaeration and makes the caking agent composition.

＜mould shearing test the making of mould 〉

With triallyl isocyanurate 12.04g, the xylene solution of platinum vinylsiloxane coordination compound (platinum that contains 3wt%) 90mg and trimethyl borate 150mg are pre-mixed stirring, make mixture A liquid.In addition, reactant (B1) 17.96g, γ-glycidoxypropyltrime,hoxysilane 750mg and the 1-ethynyl-1-hexalin 90mg with synthesis example 1 is pre-mixed stirring, making mixture B liquid.Mix said mixture A liquid and mixture B liquid and stir deaeration and become equal mixture.

With this all mixture curtain coating sandwich between with two glass sheets on the unit that the thick silicone rubber plate of 3mm makes as pad.In hot air dryer,, heat after fixing under 150 ℃/1 hour 180 ℃/30 minutes the condition at 60 ℃/6 hours, 70 ℃/1 hour, 80 ℃/1 hour, 120 ℃/1 hour.The transparent molding that will obtain with glass cutter is cut into 3mm (indulging) * 3mm (horizontal stroke) * 1mm (thick) as mould.

(measuring example 1)

The test film that embodiment 4, comparative example 1 obtain is estimated cementability by the mould shearing test.The bonding test machine 2400 of universal type that the mould shear testing maschine uses デイジ society to make.Under 23 ℃, use the load cell of 50kgf, 83 μ m/ carried out under second in trial speed.The results are shown in table 1.

(measuring example 2)

To the test film that embodiment 4, comparative example 1 obtain,, implement light fastness test in the state of bonding plane with rayed by mould.Light fastness test uses the super xenon lamp type Weatherometer of Suga trier manufacturing at radiant flux density 0.18kW/m ², Continuous irradiation 1 hour 42 minutes, the round-robin test of rainfall in 18 minutes 63 ℃ of blackboard thermoscope temperature, under the test conditions of humidity 50%, was carried out 330 hours.Test film behind the light fastness test is estimated cementability by the mould shearing test under the condition same with measuring example 1.The results are shown in table 1.

Table 1

	The mould shearing experiment
	The mould shearing experiment					Stick with paste thick, μ m	Initial stage, kgf	Stick with paste thick, μ m	After the illumination, kgf
Embodiment 1	Thin (27)	21	Thin (24)	21		Stick with paste thick, μ m	Initial stage, kgf	Stick with paste thick, μ m	After the illumination, kgf
	Thin (27)	21	Thin (24)	21	Thick (110)	27	Thick (119)	35
	Embodiment 2	Thin (22)	19	Thin (23)	Thick (110)	27	Thick (119)	35	18
Thick (125)		Thin (22)	19	Thin (23)	33	Thick (113)	35		18
Thick (125)		Embodiment 3	Thin (12)	3	33	Thick (113)	35	Thin (21)	3
Thick (125)	7		Thin (12)	3	Thick (131)	8		Thin (21)	3
Thick (125)	7		Comparative example 1	-	Thick (131)	8	23	-	15

^*) mould shearing experiment: n=5, trial value is for after removing max min, and n=3's is average.

Can learn clearly that from table 1 light-shielding paste of the present invention does not find that the cementability behind the light fastness test reduces, and has light shielding ability.In addition, can be not painted behind the light fastness test yet, have high-light-fastness.Therefore, solidification compound of the present invention can be suitable as the light-shielding paste use.

(synthesis example 2)

The mixture that uses triallyl isocyanurate 54.51g and diallyl list glycidyl chlorinated isocyanurates 87.03g is as (A) composition, the reactant of synthesis example 1 (B1) 162.64g is as (B) composition, as (D) composition, trimethyl borate 1.52g is as (E) composition as (C) composition, γ-glycidoxypropyltrime,hoxysilane 7.60g for the xylene solution of platinum vinylsiloxane coordination compound (platinum that contains 3wt%) 913mg.With above-mentioned (A) composition, (C) composition and (E) composition be pre-mixed stirring, make mixture A liquid.In addition, above-mentioned (B) composition, (D) composition and 1-ethynyl-1-hexalin 913mg is pre-mixed stirring, makes mixture B liquid.

(embodiment 5)

Mixture A liquid 114g and mixture B liquid 136g that synthesis example 2 is made stirred 10.5 minutes with planetary stirring deaeration machine (Network ラボウ (strain), マゼ Le ス one KK-500).Titanium oxide (the former industry of stone (strain), イプ one Network R-820) 250g to wherein adding as (F) composition stirred 2 minutes with planetary stirring deaeration machine.To silicon-dioxide (Japanese アェロジ Le (strain), the アェロジ Le 300) 7.5g that wherein adds as (G) composition, carry out mixing in 120 minutes, obtain solidification compound.

The viscosity (0.5rpm/1rpm) of this solidification compound by E type viscometer determining is 46Pas/31Pas.This solidification compound 150mg position coating apart from the about 1cm of glass plate edge on the thick blue sheet glass of 10cm * 10cm * 3mm is circular.As top, 80 ° the angle of tilting is placed in the stove that is heated to 100 ℃ the part of this sheet glass coating.After 1 hour, solidification compound is no longer mobile, and curtain coating is 0cm.

(embodiment 6)

Mixture A liquid 363g and mixture B liquid 434g that synthesis example 2 is made stirred 3 minutes with dissolver.Titanium oxide (the former industry of stone (strain), イプ one Network R-820) 800g to wherein adding as (F) composition stirred 14 minutes with dissolver.To silicon-dioxide (Japanese アェロジ Le (strain), the ァェロジ Le 300) 24g that wherein adds as (G) composition, carry out mixing in 49 minutes, obtain solidification compound.

The viscosity (0.5rpm/1rpm) of this solidification compound by E type viscometer determining is 39Pas/26Pas.This solidification compound 150mg position coating apart from the about 1cm of glass plate edge on the thick blue sheet glass of 10cm * 10cm * 3mm is circular.As top, 80 ° the angle of tilting is placed in the stove that is heated to 100 ℃ the part of this sheet glass coating.After 1 hour, solidification compound is no longer mobile, and curtain coating is 0cm.

(embodiment 7)

Titanium oxide (the former industry of stone (strain) that adds mixture A liquid 46g and conduct (F) composition of synthesis example 2 making, イプ one Network R-820) silicon-dioxide (the Japanese ァェロジ Le (strain) of 46g and conduct (G) composition, ァェロジ Le 300) 1.4g stirs with planetary stirring deaeration machine.In addition, titanium oxide (the former industry of stone (strain) that adds mixture B liquid 55g and conduct (F) composition, イプ one Network R-820) silicon-dioxide (Japanese アェロジ Le (strain), the アェロジ Le 300) 1.7g of 55g and conduct (G) composition stirs with planetary stirring deaeration machine.With mixed liquor A liquid-titanium oxide-silica mixture 30.0g with mixed liquid B liquid-titanium oxide-silica mixture 35.7g, mix with stirring the deaeration machine.

The viscosity (0.5rpm/2.5rpm) of this solidification compound by E type viscometer determining is 17Pas/12Pas.This solidification compound 150mg position coating apart from the about 1cm of glass plate edge on the thick blue sheet glass of 10cm * 10cm * 3mm is circular.As top, 80 ° the angle of tilting is placed in the stove that is heated to 100 ℃ the part of this sheet glass coating.After 1 hour, solidification compound can flow, and curtain coating is 9cm or more than the 9cm.

(embodiment 8)

Add the mixture A liquid 46g of synthesis example 2 making and silicon-dioxide (Japanese ァェロジ Le (strain), the ァェロジ Le 300) 3g of conduct (G) composition, stir with planetary stirring deaeration machine.In addition, titanium oxide (the former industry of stone (strain), the イプ one Network R-820) 100g that adds mixture B liquid 54g and conduct (F) composition stirs with planetary stirring deaeration machine.With mixed liquor A liquid-silica mixture 30.2g and mixed liquid B liquid-titania mixture 95.9g, mix with stirring the deaeration machine.

The viscosity (0.5rpm/1.0rpm) of this solidification compound by E type viscometer determining is 17Pas/12Pas.This solidification compound 150mg position coating apart from the about 1cm of glass plate edge on the thick blue sheet glass of 10cm * 10cm * 3mm is circular.As top, 80 ° the angle of tilting is placed in the stove that is heated to 100 ℃ the part of this sheet glass coating.After 1 hour, solidification compound can flow, and curtain coating is 9cm or more than the 9cm.

(embodiment 9)

Titanium oxide (the former industry of stone (strain) that adds mixture B liquid 54g and conduct (F) composition of synthesis example 2 making, イプ one Network R-820) silicon-dioxide (the Japanese ァェロジ Le (strain) of 100g and conduct (G) composition, ァェロジ Le 300) 3g stirs with planetary stirring deaeration machine.Mixture A liquid 22.5g and mixture B liquid-titanium oxide-thermal silica mixture 77.5g with synthesis example 2 is made mix with stirring the deaeration machine.

The viscosity (1.0rpm/2.5rpm) of this solidification compound by E type viscometer determining is 9Pas/10Pas.This solidification compound 150mg position coating apart from the about 1cm of glass plate edge on the thick blue sheet glass of 10cm * 10cm * 3mm is circular.As top, 80 ° the angle of tilting is placed in the stove that is heated to 100 ℃ the part of this sheet glass coating.After 1 hour, solidification compound can flow, and curtain coating is 9cm or more than the 9cm.

(embodiment 10)

The mixture that uses triallyl isocyanurate 54.51g and diallyl list glycidyl chlorinated isocyanurates 87.03g is as (A) composition, the reactant of synthesis example 1 (B1) 162.64g is as (B) composition, as (D) composition, trimethyl borate 1.52g is as (E) composition as (C) composition, γ-glycidoxypropyltrime,hoxysilane 7.60g for the xylene solution of platinum vinylsiloxane coordination compound (platinum that contains 3wt%) 913mg.With above-mentioned (A) composition, (C) composition and (E) composition be pre-mixed stirring, make mixture A liquid.In addition, above-mentioned (B) composition, (D) composition and 1-ethynyl-1-hexalin 90mg is pre-mixed stirring, makes mixture B liquid.Mix said mixture A liquid and mixture B liquid and stir deaeration and become equal mixture.Mix titanium oxide (the former industry of stone (strain), the イプ one Network R-820) 2.5g as (F) composition in this mixture 2.5g, remix silicon-dioxide (Japanese アェロジ Le (strain), アェロジ Le R812) 25mg stirs deaeration and obtains light-shielding paste.

(embodiment 11)

In equal the mixture 2.5g of (A)～(E) composition that embodiment 10 obtains, mix titanium oxide (the former industry of stone (strain) as (F) composition, イプ one Network R-820) 0.625g, remix silicon-dioxide (Japanese ァェロジ Le (strain), ァェロジ Le R812) 250mg also stirs deaeration and obtains light-shielding paste.

(embodiment 12)

Use triallyl isocyanurate 12.04g as (A) composition, the reactant of synthesis example 1 (B1) 17.96g is as (B) composition, as (D) composition, trimethyl borate 150mg is as (E) composition as (C) composition, γ-glycidoxypropyltrime,hoxysilane 750mg for the xylene solution of platinum vinylsiloxane coordination compound (platinum that contains 3wt%) 90mg.With above-mentioned (A) composition, (C) composition and (E) composition be pre-mixed stirring, make mixture A liquid.In addition, above-mentioned (B) composition, (D) composition and 1-ethynyl-1-hexalin 90mg is pre-mixed stirring, makes mixture B liquid.Mix said mixture A liquid and mixture B liquid and stir deaeration and become equal mixture.In this mixture 2.5g, mix titanium oxide (the former industry of stone (strain) as (F) composition, イプ one Network R-820) 2.5g, remix is as silicon-dioxide (Japanese ァェロジ Le (strain), the ァェロジ Le R812) 188mg of (G) composition and stir deaeration and obtain light-shielding paste.

(embodiment 13)

The set time of the light-shielding paste that mensuration embodiment 11 obtains.Under 115 ℃, be 32 seconds the set time of regulating timing with locking key, is the light-shielding paste that goes for the formation method of light-shielding resin layer of the present invention.

(embodiment 14)

The light-shielding paste 50mg of embodiment 10～12 record is after coating on the sheet glass becomes the circle of 8mm diameter, fixing with this sheet glass 80 degree that tilt, be determined at 21 ℃ of distances that flow down when keeping 10 minutes down.Embodiment 10:2cm.Embodiment 11:2cm, embodiment 12:2.5cm is the light-shielding paste that goes for the formation method of light-shielding resin layer of the present invention.

(embodiment 15)

With the light-shielding paste 50mg of embodiment 10～12 record in coating on the sheet glass for after the circle of 8mm diameter, this sheet glass 80 degree that tilt are fixing, be determined at 60 ℃ of distances that flow down when keeping 5 minutes down.Embodiment 10:4.5cm.Embodiment 11:3.5cm, embodiment 12:4.0cm is the light-shielding paste that goes for the formation method of light-shielding resin layer of the present invention.

(embodiment 16)

As liner, under 21 ℃, on sheet glass, be coated with the light-shielding paste that embodiment 10～12 puts down in writing with the polyester adhesive tape of 50 μ m with glass stick.In the one side opposite resinous LED shell (about 3 * 2 * 1mm is thick) is installed with double sticky tape in advance with the shell peristome.10 LED shells are a test unit.With the peristome of this shell on 21 ℃ of light-shielding pastes that are being coated on time driving fit in about 1 second down on the above-mentioned sheet glass.Heated 5 minutes in 60 ℃ hot air dryer with the state that the shell peristome is made progress.

The light-shielding paste that embodiment 10～12 obtains does not find that light-shielding paste only is coated on the side of the peristome of this shell to the electrode part bottom surface of shell bottom surface curtain coating, forms light-shielding resin.In addition, be coated with the needed time in 6 minutes or 6 minutes.

(comparative example 2)

With embodiment 16 in the same LED that uses with shell on, the light-shielding paste that obtains with pin coating embodiment 10～12.Significantly, 10 all only being coated with in the side, needing more than 30 minutes or 30 minutes, and operator's skill level is had very big dependence, in addition, is the operation that makes eyestrain very easily, is not the method that can bear mass production.

Therefore, the formation method of light-shielding resin layer of the present invention is efficiently, and is related to and boosts productivity.

(embodiment 17)

At first, as semiconductor element, on the sapphire substrate, form the nitride semiconductor layer contain n type layer, active coating and p type layer successively, a part of removing active coating and p type layer is exposed the part of n type layer.Form the p electrode on n electrode, the p type layer forming on the n type layer that this exposes, formation can be launched the luminous element of gallium nitride compound semiconductor of blue light that the monochromaticity glow peak is the 475nm of visible light.

In addition, use thermoplastic resin (polyphthalamide) by the high reflectionization of pigment such as titanium oxide as shell (housing) material, making shell molding.Promptly, in polyphthalamide resin 100 weight parts, add the thermo-stabilizer that adds trace as glass fibre 40 weight parts of strengthening material, in as titanium oxide 20 weight parts of pigment, it is one-piece type carrying out mixing and silver plated lead frame material injection forming.

The shell molding that obtains is the rectangular shape of vertical 3.5mm, horizontal 2.8mm, high 2.0mm.The shell molding has the recess of opening, in the bottom surface of this recess luminous element is installed.The opening portion of the recess of shell molding is the roughly rectangle of vertical 3.1mm, horizontal 2.4mm.The peristome sidewall of the recess of shell molding forms the taper of wide-mouth.Inject sealing resin and curing according to covering the luminous element ground of installing to recess.The shell molding has according to an end and inserts in the shell molding, the pair of lead wires electrode that the other end forms from the outside wall surface of shell molding with highlighting.The part in the front of lead-in wire electrode is exposed by the bottom surface of the 2nd recess respectively.

Luminous element is carried out chips welding (die bond) and be fixed in the shell molding recess with Resins, epoxy.The Au line that is used as the conductive metal line is at each electrode of luminous element and respectively go between and be electrically connected by lead-in wire respectively between electrode.

Then, as height reflection coating material that the solidification compound that embodiment 6 obtains is also dry according to the sidewall of the recess that is not coated on the shell molding touch luminous element, under about 100 ℃, solidified about 1 hour.

In addition, from the top of shell molding recess, inject sealing resin as the combination of the mixture A liquid 10g that contains synthesis example 2 of sealing material and mixture B liquid 11.9g.It is solidified under 60 ℃ about 6 hours, 70 ℃ about 1 hour, 80 ℃ about 1 hour, 120 ℃ about 1 hour, 150 ℃ about 1 hour, 180 ℃ about conditions of 0.5 hour, make photodiode as semiconductor device.

(comparative example 3)

Except that not the high reflection of the recess coating coating material of shell molding, with the above embodiments 17 same photodiodes of making.

(measuring example 3)

The optical output power of the photodiode that mensuration obtains, as shown in table 2, when passing through the electric current of 20mA, the photodiode of embodiment 17 obtains the roughly optical output power about 5800 μ W, but the photodiode of comparative example 3 only obtains the optical output power about about 4670 μ W under similarity condition.Can confirm that thus the photodiode of embodiment 17 is compared with the photodiode of comparative example 3, can seek the optical output power at the initial stage of improving.

Table 2

	Embodiment 17	Comparative example 3
	Embodiment 17	Comparative example 3	Optical output power	5800μW	4670μW

In addition, the photodiode of making in embodiment 17 and the comparative example 3 is carried out the soft heat actual installation repeatedly under 260 ℃, measure respectively the decline of the optical output power at initial stage as 100 o'clock optical output power.Its result as shown below.

Table 3

	Initial stage	The 1st time	The 2nd time	The 3rd time
	Initial stage	The 1st time	The 2nd time	The 3rd time	Embodiment 17	100	92.6	86.8	83.5
Comparative example 3	100	87.7	81.4	76.6	Embodiment 17	100	92.6	86.8	83.5

As can be recognized from Table 3, in embodiment 17, by forming high reflection coating material, the flavescence of the reflecting part that the heating in the time of can suppressing soft heat causes can suppress output rating and reduce.

Industrial practicality

Therefore solidification compound of the present invention can be used as light-shielding paste and uses owing to have excellent light-proofness, high-light-fastness. In addition, solidification compound of the present invention therefore by using this solidification compound, can obtain only forming with the sidewall of shell at LED the light emitting diode of solidfied material owing to have lazy flow. Have again, according to the formation method of light-shielding resin layer of the present invention, can be efficiently only be coated with light-shielding paste at LED with the sidewall of shell, and form the light-shielding resin layer, increase substantially productivity ratio.

Claims

1. light-shielding paste, neccessary composition as this light-shielding paste contains, (A) contain 2 in 1 molecule at least and have the organic compound of reactive carbon-to-carbon double bond with the SiH base, (B) contain the silicon compound of 2 SiH bases in 1 molecule at least, (C) hydrosilylation catalysts, (D) silane coupling agent and/or contain the compound of epoxy group(ing), (E) silanol condensation catalyst and (F) titanium oxide, wherein, above-mentioned (F) titanium oxide is a rutile-type, and its median size is 0.1～1.0 μ m.

2. the light-shielding paste of putting down in writing according to claim 1, wherein, (A) composition is the mixture of triallyl isocyanurate and single glycidyl diallyl chlorinated isocyanurates, (B) composition is 1,3,5, the reaction product of 7-tetramethyl-ring tetrasiloxane and triallyl isocyanurate.

3. the light-shielding paste of putting down in writing according to claim 1, wherein, (E) composition is at least a kind that selects from the group that comprises boric acid three Octadecane base esters, boric acid three n-octyls, tri-n-butyl borate, triisopropyl borate ester, boric acid three n-propyls, triethyl borate and trimethyl borate.

4. the light-shielding paste of putting down in writing according to claim 2, wherein, (E) composition is at least a kind that selects from the group that comprises boric acid three Octadecane base esters, boric acid three n-octyls, tri-n-butyl borate, triisopropyl borate ester, boric acid three n-propyls, triethyl borate and trimethyl borate.

5. according to any light-shielding paste of being put down in writing in the claim 1～4, wherein, also contain (G) silicon-dioxide.

6. the light-shielding paste of putting down in writing according to claim 5, wherein, the median size of the primary particle of above-mentioned (G) silicon-dioxide is 3～20nm.

7. the light-shielding paste of putting down in writing according to claim 5, wherein, on the glass basis material of the angles of 80 degree that tilt, under 100 ℃, through the curtain coating of the light-shielding paste after 1 hour at 2cm or below the 2cm.

8. the light-shielding paste of putting down in writing according to claim 6, wherein, on the glass basis material of the angles of 80 degree that tilt, under 100 ℃, through the curtain coating of the light-shielding paste after 1 hour at 2cm or below the 2cm.

9. the light-shielding paste of putting down in writing according to claim 5, this light-shielding paste are in having mixed the mixture of ingredients of (A) composition～(E), mix (F) composition and (G) composition and making.

10. light-shielding resin, this light-shielding resin are to solidify any light-shielding paste of being put down in writing of claim 1～9 and make.

11. a LED shell is characterized in that, in fact only has the light-shielding resin that claim 10 is put down in writing at LED with the sidewall of the peristome of shell.

12. the LED shell according to claim 11 is put down in writing is characterized in that the LED shell is resinous.

13. the LED shell according to claim 11 is put down in writing is characterized in that, LED is the composition that contains the semicrystalline polymeric resin with the shaping resin of shell.

14. the LED shell according to claim 11 is put down in writing is characterized in that, the LED shell is the pottery system.

15. the LED shell according to claim 11 is put down in writing is characterized in that, LED is a rectangle with the peristome of shell.

16. the LED shell according to claim 11 is put down in writing is characterized in that, LED is circular with the peristome of shell.

17. the LED shell according to claim 11 is put down in writing is characterized in that, LED is oval with the peristome of shell.

18. semiconductor device, this device has LED shell and luminous element, described LED possesses the peristome that comprises bottom surface and sidewall with shell, and in the peristome bottom surface, each end of positive outer electrode and the outer electrode of bearing, obtain by the shaping resin monolithic molding according to the interval of separating regulation with exposing, described luminous element is arranged at LED with on the bottom surface of shell, this semiconductor device is characterised in that, in fact only this LED with the sidewall of shell on any light-shielding paste of being put down in writing and/or form light-shielding resin that claim 10 puts down in writing and shading in the coating claim 1～9.

19. according to the semiconductor device that claim 18 is put down in writing, wherein, the shaping resin of shell is the composition that contains the semicrystalline polymeric resin.

20. semiconductor device, this device has LED shell and luminous element, described LED possesses the peristome that comprises bottom surface and sidewall with shell and in the peristome bottom surface, each end of positive outer electrode and the outer electrode of bearing, obtain by the shaping resin monolithic molding according to the interval of separating regulation with exposing, described luminous element is arranged at LED with on the bottom surface of shell, this semiconductor device is characterised in that the LED around luminous element forms light-shielding resin and shading with the bottom surface and the sidewall of shell; Wherein said light-shielding resin is made for the light-shielding paste that curing claim 1-9 is put down in writing.