CN103842442A - Curable resin composition, tablet of curable resin composition, molded body, semiconductor package, semiconductor component and light emitting diode - Google Patents
Curable resin composition, tablet of curable resin composition, molded body, semiconductor package, semiconductor component and light emitting diode Download PDFInfo
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- CN103842442A CN103842442A CN201280049280.4A CN201280049280A CN103842442A CN 103842442 A CN103842442 A CN 103842442A CN 201280049280 A CN201280049280 A CN 201280049280A CN 103842442 A CN103842442 A CN 103842442A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
- H01L23/296—Organo-silicon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14639—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles for obtaining an insulating effect, e.g. for electrical components
- B29C45/14655—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles for obtaining an insulating effect, e.g. for electrical components connected to or mounted on a carrier, e.g. lead frame
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
Abstract
The purpose of the present invention is to provide a curable composition that has a low linear coefficient of expansion and that can provide a tough cured product. The curable resin composition which is characterized by containing, as essential ingredients, (A) a silicide that has a molecular weight less than 1000 that contains at least two carbon-carbon double bonds, which are reactive with an SiH group, in each molecule, (B) a compound that contains at least two SiH groups in each molecule, (C) a hydrosilylation catalyst, (D) a silicone compound that has a molecular weight of 1000 or more and contains at least one carbon-carbon double bond, which is reactive with an SiH group, in each molecule, and (E) an inorganic filler.
Description
Technical field
The present invention relates to a kind of curable resin composition, curable resin composition flap, molding, semi-conductive encapsulation, semiconductor device and photodiode.
Background technology
All the time, in semi-conductor, apply the encapsulation that uses the curable resin that has different shape.In such encapsulation, for the electrical connection of semi-conductor and package outside, for the intensity remaining potted, or for by the thermal conduction being produced by semi-conductor to package outside etc., can use various metallic substance, to carry out integrally formed situation in the majority with curable resin.
But, the coefficient of linear expansion of resin is conventionally larger, coefficient of linear expansion is difficult to mate with the metallic substance conventionally with less coefficient of linear expansion, therefore, during in the time that heating is shaped, when after fixing or as semiconductor device, follow in the operation of various heating-cooling, produce sometimes warpage, peel off, break, to problems such as semi-conductive infringements.Especially about following the unmatched warpage of linear expansion, also have by so that the mode of the two sides equalization of metal forms to curable resin the method that warpage reduces of seeking.
But, because increasing, the heat being produced by semi-conductor in recent years requires the design that exothermicity is high, for heat being exported to effectively to the outside of encapsulation, use the package design (patent documentation 1,2) as the metal of bonding semiconductor element forms the bottom surface encapsulating.In this situation, cannot realize warpage as above and reduce, the problem of warpage becomes important.
Up to now, about reducing the warpage being caused by resin, taked the linear expansion by reducing resin to approach the countermeasure such as linear expansion, the Young's modulus of reduction resin of carrying out integrally formed metal.But while filling mineral filler in large quantities in order to reduce linear expansion, mobility when ester moulding reduces, infringement forming process; therefore, there is boundary in the method, in addition; while reducing Young's modulus, the strength decreased of resin, can damage the major function as the encapsulation of protection semiconductor element.In view of said circumstances, seek to obtain the curable resin that can reduce warpage and tough and tensile cured article in semi-conductive encapsulation.
On the other hand, the heat (also having light in the situation that semi-conductor is photodiode) being produced by semi-conductor increases, thereby further requires the thermotolerance (photostabilization) of semi-conductive encapsulation resin.For these requirements, can apply thermotolerance high, by hydrosilylation reactions and curing resin as semi-conductive resin (patent documentation 1,3) for encapsulation.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2010-62272 communique
Patent documentation 2: TOHKEMY 2009-302241 communique
Patent documentation 3: TOHKEMY 2005-146191 communique
Summary of the invention
Therefore, problem of the present invention is, the curable resin composition that provides a kind of acquisition to there is low coefficient of linear expansion and tough and tensile cured article, and provide a kind of and use said composition and metal to carry out that integrally formed warpage reduces and the semi-conductive encapsulation of tenacity excellent and use the semi-conductor of its manufacture.
In order to solve described problem, the inventor etc. concentrate on studies, found that, by form curable resin composition take following substances as essential component, can realize above-mentioned problem, thereby completed the present invention, described material is: (A) in 1 molecule, contain at least 2 molecular weight that have reactive carbon-to-carbon double bond with SiH base lower than 1000 silicon compound; (B) compound that contains at least 2 SiH bases in 1 molecule; (C) hydrosilylation catalysts; (D) in 1 molecule, contain at least 1 and there is reactive carbon-to-carbon double bond with SiH base and molecular weight is more than 1000 silicoorganic compound; And (E) inorganic filling material.
, the present invention has following formation.
(1). a kind of curable resin composition, it is characterized in that, contain following substances as essential component:
(A) in 1 molecule, contain at least 2 molecular weight that there is reactive carbon-to-carbon double bond with SiH base lower than 1000 silicon compound;
(B) compound that contains at least 2 SiH bases in 1 molecule;
(C) hydrosilylation catalysts;
(D) in 1 molecule, contain at least 1 and there is reactive carbon-to-carbon double bond with SiH base and molecular weight is more than 1000 silicoorganic compound; And
(E) inorganic filling material.
(2). the curable resin composition as described in (1), it also contains (Z) and in 1 molecule, contains at least 2 and have the organic compound of reactive carbon-to-carbon double bond with SiH base.
(3). the curable resin composition as described in (1) or (2), wherein, (D) composition is the straight chain shape polysiloxane that end has vinyl.
(4). the curable resin composition as described in any one in (1)～(3), wherein, (D) weight-average molecular weight of composition is more than 2,000 and is below 1,000,000.
(5). the curable resin composition as described in any one in (1)～(4), wherein, (E) composition is spherical silicon dioxide.
(6). the curable resin composition as described in any one in (1)～(5), it also contains (F) white pigment.
(7). the curable resin composition as described in (6), wherein, (F) median size of composition is below 1.0 μ m.
(8). the curable resin composition as described in (6) or (7), wherein, (F) composition is titanium oxide.
(9). the curable resin composition as described in (8), wherein, (F) composition is for utilizing organo-siloxane to carry out surface-treated titanium oxide.
(10). the curable resin composition as described in (8), wherein, (F) composition is for having carried out surface-treated titanium oxide with mineral compound.
(11). the curable resin composition as described in (10), wherein, (F) composition is for having carried out surface-treated titanium oxide with aluminum compound.
(12). the curable resin composition as described in (6) or (7), wherein, (F) composition is at least one being selected from zinc oxide, zirconium white, strontium oxide, niobium oxides, boron nitride, barium titanate and barium sulfate.
(13). the curable resin composition as described in any one in (1)～(12), it also contains (G) metallic soap.
(14). the curable resin composition as described in (13), wherein, (G) composition is Metallic stearates.
(15). the curable resin composition as described in (14), wherein, (G) composition be selected from calcium stearate, Magnesium Stearate, Zinic stearas, aluminum stearate more than a kind.
(16). the curable resin composition as described in any one in (1)～(15), wherein, (D) weight of composition with respect to (A) composition and (B) weight of the total of composition be more than 30 % by weight.
(17). the curable resin composition as described in any one in (1)～(16), wherein, (E) more than the amount of the total of composition accounts for 70 % by weight of curable resin composition entirety.
(18). the curable resin composition as described in any one in (6)～(17), wherein, F) content of composition be account for 10 % by weight of curable resin composition entirety more than.
(19). the curable resin composition as described in any one in (13)～(18), wherein, (G) content of composition accounts for 0.01～5 % by weight in curable resin composition entirety.
(20). the curable resin composition as described in any one in (1)～(19), wherein, the surperficial reflection of light rate that is 480nm to wavelength of solidifying the molding forming is more than 80%.
(21). the curable resin composition as described in (20), wherein, the conservation rate of the luminous reflectance factor after the oven test of 180 ℃, 24 hours (luminous reflectance factor × 100 at the luminous reflectance factor/initial stage after oven test) is more than 90%.
(22). the curable resin composition as described in any one in (1)～(21), it is characterized in that, solidify the flexural strength of the molding forming at 20N/mm
2～50N/mm
2scope in.
(23). the curable resin composition as described in any one in (2)～(22), it is characterized in that, make the composition of (A) composition～(C) and (Z) Tg of the mixture thermofixation of composition and the cured article that obtains in the scope of 30 ℃～100 ℃.
(24). the curable resin composition as described in (23), it is characterized in that, make the composition of described (A) composition～(C) and (Z) in storage elastic modulus that the mixture thermofixation of composition and the cured article that obtains are measured under the frequency 10Hz of 150 ℃, the stretch mode scope at 20MPa～100MPa.
(25). the curable resin composition as described in any one in (1)～(24), wherein, be shaped and while having made encapsulation at the one side of the effective lead frame of light-emitting diodes, the warpage of encapsulation is ± below 1.0mm.
(26). the curable resin composition as described in any one in (1)～(25), it is for semi-conductive encapsulation.
(27). a kind of flap, it is made up of the curable resin composition described in any one in (6)～(26), and described flap is characterised in that,
(A) composition and (B) viscosity when at least one party of composition is 23 ℃ be the liquid below 50Pa second,
(E) composition and (F) content of the total of composition be 70～95 % by weight,
Particle below 12 μ m account for (E) composition and (F) ratio of the total of composition be more than 40 volume %.
(28). a kind of molding, it is characterized in that, the curable resin composition described in any one in (1)～(25) is solidified and formed, and the reflection of light rate to wavelength 480nm on surface is more than 90%.
(29). a kind of semi-conductive encapsulation, it is characterized in that, use (26) described curable resin composition be shaped and obtain.
(30). a kind of semi-conductive encapsulation, it is characterized in that, use (26) described curable resin composition and metal integrally formed and obtain.
(31). the semi-conductive encapsulation as described in (29) or (30), wherein, utilizes transfer mould integrally formed and obtain curable resin composition and lead frame.
(32). the semi-conductive encapsulation as described in any one in (29)～(31), its encapsulation for forming at the one side shaping resin of metal in fact.
(33). a kind of semi-conductive encapsulation, it is to use (26) described curable resin composition to carry out transfer mould to form.
(34). a kind of semiconductor device, it uses the semi-conductive encapsulation described in any one in (29)～(33) to manufacture.
(35). a kind of photodiode, it uses the semi-conductive encapsulation described in any one in (29)～(33) to manufacture.
If adopt curable resin composition of the present invention, can obtain obtaining the curable resin composition with low coefficient of linear expansion and tough and tensile cured article, therefore, can make and use this curable resin composition and metal to carry out the semi-conductive encapsulation of the integrally formed warpage minimizing obtaining, tenacity excellent and the semi-conductor that uses this semi-conductive encapsulation to manufacture.
Accompanying drawing explanation
Fig. 1 is the concept map of molding.
Fig. 2 is the schematic diagram that represents the measuring method of intensity.
Embodiment
Below, the present invention is at length described.
Curable resin composition of the present invention is following curable resin composition, it is characterized in that, contains following substances as essential composition:
(A) in 1 molecule, contain at least 2 molecular weight that there is reactive carbon-to-carbon double bond with SiH base lower than 1000 silicon compound;
(B) compound that contains at least 2 SiH bases in 1 molecule;
(C) hydrosilylation catalysts;
(D) in 1 molecule, contain at least 1 there is reactive carbon-to-carbon double bond with SiH base, molecular weight is more than 1000 silicoorganic compound; And
(E) inorganic filling material.
Below, each composition is described.
((A) composition)
(A) composition, as long as containing at least 2 molecular weight that have reactive carbon-to-carbon double bond with SiH base lower than 1000 silicon compound in 1 molecule, just can be not particularly limited to use.
(A) carbon-to-carbon double bond in composition is preferably bonded directly to the CH of Siliciumatom
2the structure of=CH-Si type.Its reason is that in the time that curable resin composition of the present invention solidifies by hydrosilylation reactions, this structure is high to the reactive behavior of hydrosilylation, and does not follow side reaction, therefore, easily obtains target crosslinking structure.On the other hand, the one-tenth that is equivalent to (A) composition that for example aforesaid patent documentation 3 records is divided into the carbon-to-carbon double bond of not siliceous common organic compound, the isomerization reaction to inner alkene of the side reaction while therefore, inevitably following as hydrosilylation.Once if generate inner alkene, worry the activity of hydrosilylation reactions extremely to reduce, follow the mechanical properties that reactivity reduces to reduce, occur the unfavorable conditions such as surface viscosity.
In addition, form and make curable resin composition of the present invention solidify the Si-C key (bond length 1.91 of the crosslinking structure of the cured article forming.The distance of C-C key is 1.50.) the cured article recorded with aforementioned patent document 3 of ratio compared with increase, so, can reduce cross-linking density.Therefore, (D) described later by combining composition, compared with the cured article of patent documentation 3, can obtain low linear expansion rate and the cured article for low elasticity and tenacity excellent.
As (A) composition, from can further improving stable on heating viewpoint, preferred every 1g (A) composition contains and more than 0.001mol has reactive carbon-to-carbon double bond with SiH base, more preferably more than every 1g contains 0.003mol, more than further preferably containing 0.005mol.
For (A) composition there is the number of reactive carbon-to-carbon double bond with SiH base, average every 1 molecule be at least 2, in the situation that expecting further raising mechanical strength, preferably exceedes 2, more preferably more than 3.On the contrary, in the situation that expecting cured article to give flexibility or toughness, while reaching more than 3, fragility is remarkable sometimes, therefore, is preferably the number that on average approaches 2.(A) number that has reactive carbon-to-carbon double bond with SiH base of composition is below 1 time in every 1 molecule, even react with (B) composition, also only forms Grafting Structure, can not form crosslinking structure.
In addition, easily become good viewpoint from stability in storage, preferably in 1 molecule, contain vinyl below 6, more preferably in 1 molecule, contain vinyl below 4.
(A) molecular weight of composition is lower than 1000.The good viewpoint of few and plasticity, operability, the good viewpoint of plasticity when easily evenly mixing aspect and make curable resin composition flap with the powder such as (E) composition and (F) composition from the stringiness of the high viewpoint of mechanics thermotolerance and stock liquid, molecular weight preferably lower than 900, more preferably less than 700, further preferably lower than 500.
As (A) composition, in order evenly to mix with other composition and to obtain good operability, at 23 ℃, be preferably liquid, as its viscosity, preferably at 23 ℃ lower than 1000 pools, more preferably 500 pool below, further preferably lower than 300 pools, particularly preferably lower than 30 pools.Viscosity can utilize E type viscometer to measure.
If concrete example (A) composition, can example: CH
2=CHSiMe
2o (SiMe
2o)
nsiMe
2cH=CH
2(n=0～10), CH
2=CHSiMe
2o (SiMe
2o)
m(SiPh
2o)
nsiMe
2cH=CH
2(m=0～5, n=1～4), CH
2=CHSiPh
2o (SiMe
2o)
m(SiPh
2o)
nsiPh
2cH=CH
2(m=0～3, n=1～2), CH
2=CHSiMe
2o (SiMe
2o)
m(SiPhMeO)
nsiMe
2cH=CH
2(m=0～5, n=1～6), Me
3siO (SiMe
2o)
m(SiMe (CH=CH
2) O)
nsiMe
3(m=0～5, n=2～9), MeSi[O (SiMe
2o)
msiMe
2cH=CH
2]
3straight chain shapes such as (m=0～2), a chain silicone compounds;
1,3,5,7-tetrem thiazolinyl-1,3,5,7-tetramethyl-ring tetrasiloxane, 1,3,5-trivinyl-pentamethyl-cyclotetrasiloxane, 1,3-divinyl-hexamethyl cyclotetrasiloxane, 1,5-divinyl-hexamethyl cyclotetrasiloxane, 1,3,5,7-tetrem thiazolinyl-1-phenyl-3,5,7-trimethylammonium cyclotetrasiloxane, 1,3,5,7-tetrem thiazolinyl-1,3-phenylbenzene-5,7-dimethyl cyclotetrasiloxane, 1,3,5,7-tetrem thiazolinyl-1,5-phenylbenzene-3,7-dimethyl cyclotetrasiloxane, 1,3,5,7-tetrem thiazolinyl-1,3,5-triphenyl-7-methyl cyclotetrasiloxane, 1-phenyl-3,5,7-trivinyl-1,3,5,7-tetramethyl-ring tetrasiloxane, 1,3-phenylbenzene-5,7-divinyl-1,3,5,7-tetramethyl-ring tetrasiloxane, 1,5-phenylbenzene-3,7-divinyl-1,3,5,7-tetramethyl-ring tetrasiloxane, 1,3,5-trivinyl-1,3,5-trimethylammonium cyclotrisiloxane, 1,3,5,7,9-, five vinyl-1,3,5,7,9-pentamethyl-D5, 1,3,5,7,9,11-, six vinyl-1, the cyclic siloxane compounds such as 3,5,7,9,11-pregnancy basic ring, six siloxanes.
As the compound beyond siloxanes, can enumerate: ClCH
2cH
2cH
2siMe (CH=CH
2)
2, (CH
2=CH)
2siMe
2, (CH
2=CH)
2siPhMe, (CH
2=CH)
2siPh
2, (CH
2=CH)
2si (OEt)
2, PhSi (CH=CH
2)
3, (CH
2=CH)
4si, CH
2=CHMe
2si-C
6h
4p-SiMe
2cH=CH
2, CH
2=CHMe
2siO-C
6h
4p-OSiMe
2cH=CH
2deng.
In the compound that contains benzene (Ph) base in concrete example shown in above-mentioned, part or all of phenyl can be substituted by the following aryl of enumerating.As such aryl, for example can enumerate: naphthyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-propyl group phenyl, 3-propyl group phenyl, 4-propyl group phenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 2-butyl phenyl, 3-butyl phenyl, 4-butyl phenyl, 3-isobutyl phenenyl, 4-isobutyl phenenyl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 3-amyl group phenyl, 4-amyl group phenyl, 3-hexyl phenyl, 4-hexyl phenyl, 3-cyclohexyl phenyl, 4-cyclohexyl phenyl, 2,3-3,5-dimethylphenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, 3,4-3,5-dimethylphenyl, 3,5-3,5-dimethylphenyl, 2,3-diethyl phenyl, 2,4-diethyl phenyl, 2,5-diethyl phenyl, 2,6-diethyl phenyl, 3,4-diethyl phenyl, 3,5-diethyl phenyl, xenyl, 2,3,4-trimethylphenyl, 2，3，5-trimethylphenyl, 2，4，5-trimethylphenyl, 3-epoxy and phenyl, 4-epoxy and phenyl, 3-glycidyl phenyl, 4-glycidyl phenyl etc.These groups may be used alone, two or more kinds can also be used to use.
In above-claimed cpd, from the property obtained is good, volatility is low, with (B) composition or (D) the consistency reactivity good, that follow hydrosilylation cure of composition high, curable resin composition of the present invention is solidified and the cured article that obtains has low coefficient of linear expansion, the viewpoint such as tough and tensile, can preferably use CH
2=CHSiMe
2o (SiMe
2o)
nsiMe
2cH=CH
2(n=1～3), CH
2=CHSiMe
2oSiPh
2oSiMe
2cH=CH
2, CH
2=CHSiMe
2o (SiPh
2o)
2siMe
2cH=CH
2, CH
2=CHSiMe
2oSiPhMeOSiMe
2cH=CH
2, CH
2=CHSiMe
2o (SiPhMeO)
2siMe
2cH=CH
2, CH
2=CHSiPh
2oSiPh
2cH=CH
2, 1,3,5-trivinyl-pentamethyl-cyclotetrasiloxane, 1,3-divinyl-hexamethyl cyclotetrasiloxane, 1,5-divinyl-hexamethyl cyclotetrasiloxane, 1,3-phenylbenzene-5,7-divinyl-1,3,5,7-tetramethyl-ring tetrasiloxane, 1,3,5-trivinyl-1,3,5-trimethylammonium cyclotrisiloxane, 1,5-phenylbenzene-3,7-divinyl-1,3,5,7-tetramethyl-ring tetrasiloxane, CH
2=CHMe
2si-C6H
4p-SiMe
2cH=CH
2, CH
2=CHMe
2siO-C
6h
4p-OSiMe
2cH=CH
2.
(mixing of (A) composition)
(A) composition can use separately or two or more mixing use.
((Z) composition)
(Z) composition is in 1 molecule, to contain at least 2 to have the organic compound of reactive carbon-to-carbon double bond with SiH base, is the compound different from (A) composition.
Can be by (Z) composition with (A) composition and use.
As the concrete example of this organic compound, can enumerate: Phthalic acid, diallyl ester, trimellitic acid triallyl, diethylene glycol bis-(allyl carbonate), trimethylolpropane allyl ether, pentaerythritol triallyl ether, 1, 1, 2, 2-tetraene propoxy-ethane, diallylidene tetramethylolmethane, triallylcyanurate, cyanacrylate, diallyl list glycidyl isocyanuric acid ester, diallyl monomethyl isocyanuric acid ester, 1, 2, 4-trivinyl hexanaphthene, Vinylstyrene class (the Vinylstyrene class of purity 50～100%, the preferably Vinylstyrene class of purity 80～100%), divinyl biphenyl, 1, 3-di isopropenylbenzene, 1, 4-di isopropenylbenzene and their oligopolymer,
[Chemical formula 1]
[Chemical formula 2]
[chemical formula 3]
Aliphatics Cyclic Polyene compounds, vinyl cyclopentenes, the vinyl cyclohexene such as aliphatics chain polyenic compounds system, cyclopentadiene, cyclohexadiene, cyclooctadiene, Dicyclopentadiene (DCPD), three cyclopentadiene, norbornadiene such as divinyl, isoprene, octadiene, decadiene etc. replace aliphatics cyclic olefin compounds etc.
In these organic compound, from stable on heating viewpoint, preferably use triallylcyanurate, cyanacrylate, diallyl list glycidyl isocyanuric acid ester, diallyl monomethyl isocyanuric acid ester, 1, 2, 4-trivinyl hexanaphthene, Vinylstyrene class (the Vinylstyrene class of purity 50～100%, the preferably Vinylstyrene class of purity 80～100%), divinyl biphenyl, more preferably use triallylcyanurate, cyanacrylate, diallyl list glycidyl isocyanuric acid ester, diallyl monomethyl isocyanuric acid ester, 1, 2, 4-trivinyl hexanaphthene, further preferably use cyanacrylate, diallyl list glycidyl isocyanuric acid ester, diallyl monomethyl isocyanuric acid ester.
In addition, for and consumption during with the organic compound of above-mentioned (Z) composition, the flexibility of molding for example obtaining from the curable resin composition the present invention is formed and the viewpoint of the balance of intensity, be preferably in the scope of 5～50 weight parts with respect to (A) composition 100 weight parts, more preferably in the scope of 10～45 weight parts, more preferably in the scope of 15～40 weight parts.
((B) composition)
(B) composition is the compound that contains at least 2 SiH bases in 1 molecule.
For (B) composition, as long as the compound that contains at least 2 SiH bases in 1 molecule, just be not particularly limited, can use in the compound of recording in No. 96/15194 brochure of International Publication such as and in 1 molecule, there is compound of at least 2 SiH bases etc.
Wherein, from the property obtained aspect, preferably in 1 molecule, there is chain and/or the ring-type organopolysiloxane of at least 2 SiH bases, from the viewpoint good with the consistency of (A) composition, the further ring-type organopolysiloxane in 1 molecule with at least 2 SiH bases shown in preferred following general formula (VI).
[chemical formula 4]
(in formula, R
1the organic group that represents carbon number 1～6, n represents 3～10 number.)
Substituent R in compound shown in general formula (VI)
1be preferably the group being formed by C, H, O, more preferably alkyl, more preferably methyl.
As the compound shown in general formula (VI), from the viewpoint of easily obtaining, be preferably 1,3,5,7-tetramethyl-ring tetrasiloxane.
To the not special restriction of the molecular weight of (B) composition, can preferably use the material of any molecular weight, but from more easily manifest mobility, easily with the mixed uniformly viewpoint of powder such as (E) composition and (F) composition, preferably use low-molecular-weight material.In this case, under preferred molecular weight, be limited to 50, more preferably 100, more preferably 150.On preferred molecular weight, be limited to 100,000, more preferably 5,000, further preferably 2,000, be particularly preferably 1,500.
As (B) composition, for it is easily evenly mixed with the powder such as other composition, particularly (E) composition and (F) composition, more specifically never need to be heated to fusing point in order evenly to mix makes its liquefaction aspect set out above, at 23 ℃, be preferably liquid, as its viscosity, at 23 ℃, be preferably below 50Pa second, below more preferably 20Pa second, more preferably below 5Pa second.Viscosity can utilize E type viscometer to measure.
(B) composition can use separately or two or more is mixed and is used.
(preferred structure of (B) composition)
Be difficult to the viewpoint that produces the viewpoint of the problem that discharges gas from the curable resin composition obtaining and the cured article being obtained by said composition is given to practicality intensity, toughness from the volatility step-down of (B) composition, there is no in fact volatility, except siloxane backbone, also have and imported from the composition of the skeleton of organic compound than the compound only being formed by siloxane backbone more preferably.The manufacture method of this compound does not limit, and (B) composition is preferably that the compound (β) that has the organic compound (α) of reactive carbon-to-carbon double bond by containing more than 1 with SiH base and have at least 2 SiH bases in 1 molecule in 1 molecule carries out hydrosilylation reactions and the compound that can obtain.
((α) composition)
((α 1) composition)
As (α) composition, can use and material (α 1) that can be identical with above-mentioned (Z) composition of (A) composition use.While using (α 1) composition, the cross-linking density of the cured article obtaining uprises, and easily becomes the cured article that mechanical strength is high.
((α 2) composition)
In addition, also can use and in 1 molecule, contain 1 and there is the organic compound (α 2) of reactive carbon-to-carbon double bond with SiH base.While using (α 2) composition, the cured article obtaining easily becomes low elasticity.
As (α 2) composition, there is the organic compound of reactive carbon-to-carbon double bond as long as contain 1 in 1 molecule with SiH base, be just not particularly limited.
The bonding position that has reactive carbon-to-carbon double bond with SiH base of (α 2) composition is not particularly limited, and may reside in intramolecular optional position.
The compound of (α 2) composition can be divided into compound and the monomer compounds of polymer class.
As polymer class compound, for example can use: the compound of polysiloxane-based, polyethers, polyester, polyarylester class, polycarbonate-based, saturated hydrocarbons, unsaturated hydro carbons, polyacrylate(s), polyamide-based, P-F class (resol class), polyimide.
In addition, as monomer compounds, for example can enumerate: phenols, bisphenols, benzene, naphthalene etc. are aromatic hydrocarbon based; The aliphatic hydrocarbons such as straight chain class, alicyclic ring class; Heterocyclic compound, silicon compounds and their mixture etc.
As (α 2) composition there is reactive carbon-to-carbon double bond with SiH base, be not particularly limited, from the viewpoint of reactive, the group shown in preferred following general formula (I).
[chemical formula 5]
(in formula, R
1represent hydrogen atom or methyl.)
In addition, from obtaining the easy degree of raw material, the particularly preferably group shown in [chemical formula 6].
[chemical formula 6]
As (α 2) composition there is reactive carbon-to-carbon double bond with SiH base, high from the viewpoint of the thermotolerance of cured article, the ester ring type group shown in preferred following general formula (II).
[chemical formula 7]
(R in formula
2represent hydrogen atom or methyl.)
In addition, consider the particularly preferably ester ring type group shown in [chemical formula 8] from the easy obtaining degree of raw material.
[chemical formula 8]
There is reactive carbon-to-carbon double bond and can be bonded directly to the skeleton part of (α 2) composition with SiH base, also can carry out covalent bonding by substituting group more than divalent.As substituting group more than divalent, as long as the substituting group of carbon number 0～10, be just not particularly limited.As these substituent examples, can enumerate the substituting group shown in following.
[chemical formula 9]
(n represents 1～10 number.）
[Chemical formula 1 0]
In addition, these more than divalent more than substituent 2 can linking and form 1 substituting group more than divalent by covalent linkage.
Divide the example of the group that carries out covalent bonding as above-mentioned and skeleton portion; can enumerate: 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-,
[Chemical formula 1 1]
As the concrete example of (α 2) composition, can enumerate: as the Linearen, 4 of propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-laurylene, 1-hendecene, Idemitsu Petrochemical Co., Ltd.'s manufacture, 4-dimethyl-1-amylene, 2-methyl isophthalic acid-hexene, 2,3,3-trimethylammonium-1-butylene, 2, the chain aliphatic hydrocarbon based compound classes such as 4,4-trimethylammonium-1-amylene; The annular aliphatic hydrocarbon compound classes such as tetrahydrobenzene, tetrahydrotoluene, methylene radical hexanaphthene, norbornylene, ethylidene hexanaphthene, vinyl cyclohexane, amphene, carene, α firpene, beta pinene; As aromatic hydrocarbons based compounds such as vinylbenzene, α-methylstyrene, indenes, phenylacetylene, 4-ethynyl toluene, allyl benzene, 4-phenyl-1-butylene; The allyl ether series such as alkyl allyl ethers, allyl phenyl ether; The aliphatic category compounds such as allylin, ethylene glycol monoallyl ether, 4-vinyl-DOX-2-ketone; The aromatic series compounds classes such as 1,2-dimethoxy-4 '-allyl benzene, o-allyl phenol; Monoene propyl group dibenzyl isocyanuric acid ester, monoene propyl group diglycidyl isocyanuric acid ester etc. replace the silicon compounds such as isocyanuric acid ester class, vinyl trimethylsilane, vinyltrimethoxy silane, vinyl tri-phenyl-silane etc.And then, can also enumerate: the polyethers resins such as the polyethylene oxide of single end allylation, the poly(propylene oxide) of single end allylation; The hydrocarbon resins such as the polyisobutene of single end allylation; Single ends such as acrylic resin such as butyl polyacrylate, the polymethylmethacrylate of single end allylation of single end allylation have polymkeric substance or the oligopolymer class etc. of vinyl.
The structure of (α 2) composition can be wire, can be also branch-like, and molecular weight is not particularly limited, and can use the material of various molecular weight.Molecular weight distribution is also not particularly limited, viscosity, the plasticity of mixture easily become good aspect, molecular weight distribution is preferably below 3, more preferably below 2, more preferably below 1.5.
While there is second-order transition temperature in (α 2) composition, this second-order transition temperature is not particularly limited, can use the material of various second-order transition temperatures, the cured article obtaining easily become tough and tensile aspect, second-order transition temperature be preferably 100 ℃ following, more preferably 50 ℃ following, more preferably below 0 ℃.In such (α 2) composition, as the example of preferred resin, can enumerate butyl polyacrylate resin etc.On the contrary, aspect the thermotolerance of the cured article obtaining uprises, second-order transition temperature be preferably 100 ℃ above, more preferably 120 ℃ above, more preferably 150 ℃ above, most preferably be more than 170 ℃.Second-order transition temperature can be in Measurement of Dynamic Viscoelasticity shows that with tan δ the form of maximum temperature obtains.
As (α 2) composition, aspect the thermotolerance of the cured article obtaining uprises, be preferably hydrocarbon compound.Now preferred carbon number under be limited to 7, on preferred carbon number, be limited to 10.
As (α 2) composition, can there is other reactive group.As reactive group now, can enumerate: epoxy group(ing), amino, free-radical polymerised unsaturated group, carboxyl, isocyanate group, hydroxyl, alkoxysilyl etc.In the situation that having these functional groups, the cementability of the curable resin composition obtaining easily uprises, and the intensity of the cured article obtaining easily uprises.Become higher from the viewpoint of adhesiveproperties, preferred epoxy group(ing) in these functional groups.In addition, aspect the thermotolerance of the cured article obtaining easily uprises, preferably in average 1 molecule, there is more than 1 reactive group.Specifically can enumerate: monoene propyl group diglycidyl isocyanuric acid ester, glycidyl allyl ether, methacrylic acid allyloxy ethyl ester, vinylformic acid allyloxy ethyl ester, vinyltrimethoxy silane etc.
Or/and (α 2) composition can use single material, also can be used in combination many kinds of substance as (α 1) composition as above.
((β) composition)
(β) composition is the compound in 1 molecule with at least 2 SiH bases, and the organopolysiloxane of chain and/or ring-type is also its example.
Particularly, for example can enumerate the compound shown in [Chemical formula 1 2] and [Chemical formula 1 3].
[Chemical formula 1 2]
[Chemical formula 1 3]
At this, from easily becoming good viewpoint with the consistency of (α) composition, the cyclic polyorganosiloxane in 1 molecule with at least 3 SiH bases that preferred following general formula (VI) represents.
[Chemical formula 1 4]
(in formula, R
1the organic group that represents carbon number 1～6, n represents 3～10 number.)
Substituent R in the compound that above-mentioned general formula (VI) represents
1be preferably the group being formed by C, H, O, more preferably alkyl, more preferably methyl.
From obtaining easiness etc., (β) composition is preferably 1,3,5,7-tetramethyl-ring tetrasiloxane.
As other example of (β) composition, can enumerate two (dimetylsilyl) benzene etc. and there is the compound of SiH base.
Various (β) as above composition can use separately or two or more is mixed and is used.
((α) composition and (β) reaction of composition)
Below, about use will (α) composition and (β) (α) composition when composition carries out compound that hydrosilylation reactions can obtain as (B) composition describe with (β) hydrosilylation reactions of composition.
In addition, by (α) composition with (β) when composition carries out hydrosilylation reactions, sometimes can be contained the mixture of the multiple compounds of (B) composition, also can directly not use mixture to make curable resin composition of the present invention from wherein separating (B) composition in the situation that.
(α) composition when making (α) composition and (β) composition carrying out hydrosilylation reactions and (β) mixture ratio of composition are not particularly limited; consider by (B) composition obtaining with (A) when the intensity of cured article that the hydrosilylation of composition obtains; preferably the SiH base of (B) composition is more; the ratio of the sum (Y) of the SiH base in (β) composition that has the sum (X) of reactive carbon-to-carbon double bond with SiH base and mix in (α) composition therefore, conventionally mixing is preferably Y/X≤2, Y/X≤3 more preferably.In addition, easily improve from the viewpoint of (B) composition and (A) consistency of composition, be preferably Y/X≤10, Y/X≤5 more preferably.
In the situation that making (α) composition and (β) composition carries out hydrosilylation reactions, can use suitable catalyzer.As catalyzer, can use for example following substances.
Can enumerate: platinum simple substance, make the supported carrier solid platinum such as aluminum oxide, silicon-dioxide, carbon black and complex compound, alkene-platinum complex (for example, Pt (CH of catalyzer, Platinic chloride, Platinic chloride and alcohol of obtaining, aldehyde, ketone etc.
2=CH
2)
2(PPh
3)
2, Pt (CH
2=CH
2)
2cl
2), vinylsiloxane-platinum complex (for example, Pt (ViMe
2siOSiMe
2vi)
n, Pt[(MeViSiO)
4]
m), phosphine-platinum complex (for example, Pt (PPh
3)
4, Pt (PBu
3)
4), phosphinate-platinum complex (for example, Pt[P (OPh)
3]
4, Pt[P (OBu)
3]
4) (in formula, Me represents methyl, and Bu represents butyl, and Vi represents vinyl, and Ph represents phenyl, and n, m represent integer.), dicarbapentaborane dichloro platinum, Karst (Karstedt) catalyzer, in addition, Ash is than the platinum alkoxide catalysis of recording in No. 3220972 specification sheets of the United States Patent (USP) of hydrocarbon-platinum complexes of recording in No. 3159601st, the United States Patent (USP) of (Ashby) and No. 3159662 specification sheetss and La Moli AUX (Lamoreaux).And then platinum chloride-alkene complex of recording in No. 3516946 specification sheets of United States Patent (USP) of Mo Dike (Modic) is also useful in the present invention.
In addition, as the example of the catalyzer beyond 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.
Wherein, from the viewpoint of catalytic activity, preferably Platinic chloride, alkene-platinum complex, vinylsiloxane-platinum complex etc.In addition, these catalyzer may be used alone, two or more kinds can also be used.
Addition to catalyzer is not particularly limited, for there is sufficient solidified nature and by the cost control of curable resin composition at lower level, preferably the lower limit of addition is 10 with respect to 1 mole, the SiH base of (β) composition
-8mole, more preferably 10
-6mole, preferably the upper limit of addition is 10 with respect to 1 mole, the SiH base of (β) composition
-1mole, more preferably 10
-2mole.
In addition, can and use promotor in above-mentioned catalyzer, as the example of promotor, can enumerate: the Phosphorus compound such as triphenylphosphine, dimethyl maleate etc. 1, the aminated compoundss such as sulphur compounds, triethylamine such as alkynol compounds, the elemental sulfurs such as 2-bis-ester compounds, 2-hydroxy-2-methyl-ethyl acetylene etc.The addition of promotor is not particularly limited, with respect to being limited to 10 under the preferred addition of 1 mole of hydrosilylation catalysts
-2mole, more preferably 10
-1mole, on preferred addition, be limited to 10
2mole, more preferably 10 moles.
The blending means of (α) composition when reacting, (β) composition, catalyzer, can adopt the whole bag of tricks, the mixture preferably mixed catalyst in (α) composition being obtained is mixed in the method for (β) composition.If in the mixture of (α) composition, (β) composition the method for mixed catalyst, be difficult to control reaction.Adopting the method for mixing (α) composition in the mixture that is being mixed with (β) composition and catalyzer, because (β) composition under the existence of catalyzer and the moisture of sneaking into have reactivity, therefore, occur sometimes to go bad.
As temperature of reaction, can carry out various settings, in this case preferred temperature range under be limited to 30 ℃, more preferably 50 ℃, in preferred temperature range, be limited to 200 ℃, more preferably 150 ℃.If temperature of reaction is low, extend for the reaction times of fully reaction, if temperature of reaction is high, impracticable.Reaction can be carried out at fixing temperature, also can make as required the temperature multistage or change continuously.
Pressure when reaction times, reaction also can carry out various settings as required.
In the time of hydrosilylation reactions, can use solvent.Operable solvent only otherwise hindering hydrosilylation reactions is just not particularly limited, if concrete example can preferably be used: the varsols such as benzene, toluene, hexane, heptane; Tetrahydrofuran (THF), Isosorbide-5-Nitrae-bis-
the ether solvents such as alkane, DOX, Anaesthetie Ether; The ketones solvent such as acetone, methyl ethyl ketone; Chloroform, methylene dichloride, 1, the halogen kind solvents such as 2-ethylene dichloride.Solvent also can use with the form of mixed solvent of more than two kinds.As solvent, preferably toluene, tetrahydrofuran (THF), DOX, chloroform.The quantity of solvent using also can suitably be set.
In addition,, in order to control reactive object etc., can use various additives.
Making (α) composition and (β) after composition reaction, also can be except desolventizing or/and unreacted (α) composition or/and (β) composition.By removing these volatile components, because (B) composition obtaining does not contain volatile component, therefore, in the time solidifying with (A) composition, be difficult for producing because of volatile component the volatilize space causing, the problem of crackle.As the method for removing, for example, except decompression devolatilization, can enumerate and utilize processing that gac, pure aluminium silicate, silica gel etc. carry out etc.The in the situation that of decompression devolatilization, preferably process at low temperatures.In this case, preferred temperature on be limited to 100 ℃, more preferably 60 ℃.While at high temperature processing, easily follow thickening iso-metamorphism.
As conduct as above (α) composition and (β) example of (B) composition of the reactant of composition, can enumerate: tetrabutyl ammonium bromide and 1, 3, 5, the reactant of 7-tetramethyl-ring tetrasiloxane, vinyl cyclohexene and 1, 3, 5, the reactant of 7-tetramethyl-ring tetrasiloxane, Vinylstyrene and 1, 3, 5, the reactant of 7-tetramethyl-ring tetrasiloxane, Dicyclopentadiene (DCPD) and 1, 3, 5, the reactant of 7-tetramethyl-ring tetrasiloxane, cyanacrylate and 1, 3, 5, the reactant of 7-tetramethyl-ring tetrasiloxane, diallyl list glycidyl isocyanuric acid ester 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, α-methylstyrene and 1, 3, 5, the reactant of 7-tetramethyl-ring tetrasiloxane, monoene propyl group diglycidyl isocyanuric acid ester and 1, 3, 5, the reactant of 7-tetramethyl-ring tetrasiloxane, the reactant of vinyl norbornene and two (dimetylsilyl) benzene etc.In addition, also can enumerate: the reactant of glycidyl allyl ether, cyanacrylate and 1,3,5,7-tetramethyl-ring tetrasiloxane etc.
((A) composition and (B) mixing of composition)
For (A) composition and (B) combination of composition, can enumerate the cited material of the example of the material cited as the example of (A) composition and their various mixture/conducts (B) composition and the various combinations of their various mixtures.
For (A) composition and (B) mixture ratio of composition, only otherwise lose necessary intensity, just be not particularly limited, (B) number (Y) of the SiH base in composition is with respect to being limited to Y/X≤0.3, more preferably Y/X≤0.5, Y/X≤0.7 more preferably under the preferable range of the ratio of the number (X) of the carbon-to-carbon double bond in (A) composition, is limited to Y/X≤3, more preferably Y/X≤2, Y/X≤1.5 more preferably in preferable range.In the situation that departing from preferable range, sometimes can not obtain sufficient intensity, or easy thermal degradation when.
The in the situation that of also containing (Z) composition at curable resin composition, for (A) composition and (Z) composition and (B) mixture ratio of composition, only otherwise lose necessary intensity, just be not particularly limited, (B) number (Y) of the SiH base in composition with respect to (A) and (Z) ratio of the sum (X) of the carbon-to-carbon double bond in composition preferably be contained in above-mentioned scope.
((C) composition)
(C) composition is hydrosilylation catalysts.
As hydrosilylation catalysts, as long as there is the catalytic activity of hydrosilylation reactions, just be not particularly limited, for example can enumerate: platinum simple substance, make the supported carrier solid platinum such as aluminum oxide, silicon-dioxide, carbon black and complex compound, alkene-platinum complex (for example, Pt (CH of catalyzer, Platinic chloride, Platinic chloride and alcohol of obtaining, aldehyde, ketone etc.
2=CH
2)
2(PPh
3)
2, Pt (CH
2=CH
2)
2cl
2), vinylsiloxane-platinum complex (for example, Pt (ViMe
2siOSiMe
2vi)
n, Pt[(MeViSiO)
4]
m), phosphine-platinum complex (for example, Pt (PPh
3)
4, Pt (PBu
3)
4), phosphinate-platinum complex (for example, Pt[P (OPh)
3]
4, Pt[P (OBu)
3]
4) (in formula, Me represents methyl, and Bu represents butyl, and Vi represents vinyl, and Ph represents phenyl, and n, m represent integer.), dicarbapentaborane dichloro platinum, Karst (Karstedt) catalyzer, in addition, Ash is than the platinum alkoxide catalysis of recording in No. 3220972 specification sheets of the United States Patent (USP) of hydrocarbon-platinum complexes of recording in No. 3159601st, the United States Patent (USP) of (Ashby) and No. 3159662 specification sheetss and La Moli AUX (Lamoreaux).And then platinum chloride-alkene complex of recording in No. 3516946 specification sheets of United States Patent (USP) of Mo Dike (Modic) is also useful in the present invention.
In addition, as the example of the catalyzer beyond 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.
Wherein, from the viewpoint of catalytic activity, preferably Platinic chloride, alkene-platinum complex, vinylsiloxane-platinum complex etc.In addition, these catalyzer may be used alone, two or more kinds can also be used.
Addition to catalyzer is not particularly limited, for there is sufficient solidified nature and by the cost control of curable resin composition at lower level, preferably the lower limit of addition is 10 with respect to 1 mole, the SiH base of (B) composition
-8mole, more preferably 10
-6mole, preferably the upper limit of addition is 10 with respect to 1 mole, the SiH base of (B) composition
-1mole, more preferably 10
-2mole.
In addition, can and use promotor in above-mentioned catalyzer, as the example of promotor, can enumerate: the Phosphorus compound such as triphenylphosphine, dimethyl maleate etc. 1, the aminated compoundss such as sulphur compounds, triethylamine such as alkynol compounds, the elemental sulfurs such as 2-bis-ester compounds, 2-hydroxy-2-methyl-ethyl acetylene etc.The addition of promotor is not particularly limited, with respect to being limited to 10 under the preferred addition of 1 mole of hydrosilylation catalysts
-2mole, more preferably 10
-1mole, on preferred addition, be limited to 10
2mole, more preferably 10 moles.
(make (A)～(C) and (Z) the mixture thermofixation of composition and the proterties of the cured article that obtains)
In addition, from taking into account the resistance to bend(ing) of the curable resin composition the present invention and the viewpoint of continuous molding, make (A)～(C) and (Z) the mixture thermofixation of composition and the cured article that obtains second-order transition temperature (Tg) preferably in the scope of 30 ℃～100 ℃, more preferably in the scope of 35 ℃～80 ℃, further preferably in the scope of 40 ℃～70 ℃.The Tg of this cured article is during lower than 30 ℃, and continuous molding is sometimes poor, when Tg exceedes 100 ℃, sometimes damages the resistance to bend(ing) of molding.
In addition, from the same viewpoint, make (A)～storage elastic modulus that (C) and (Z) the mixture thermofixation of composition and the cured article that obtains are measured under 150 ℃, frequency 10Hz, stretch mode preferably in the scope at 20MPa～100MPa, more preferably in the scope at 25MPa～80MPa, further preferably in the scope at 30MPa～70MPa.The storage elastic modulus of this cured article is during lower than 20MPa, and continuous molding variation sometimes, when storage elastic modulus exceedes 100MPa, damages the flexibility of cured article sometimes.
Make above-mentioned (A)～(C) and (Z) the mixture thermofixation of composition and the Tg of cured article and the method for storage elastic modulus that obtain as mensuration, can enumerate for example Measurement of Dynamic Viscoelasticity device (IT Meter & Controls, Inc. DVA200 processed, stretch mode, mensuration frequency 10Hz).At this, second-order transition temperature is set as the peak temperature of loss tangent.
((D) composition)
(D) composition is that in 1 molecule, to contain at least 1 molecular weight that has reactive carbon-to-carbon double bond with SiH base be more than 1000 silicoorganic compound.By using the silicoorganic compound that formed by the siloxane backbone that comprises Si-O-Si key in fact, compared with using the high molecular situation of common organic system, can obtain the cured article of thermotolerance, excellent in light-resistance.And then, by using (D) composition, in the time mixing with the inorganic filling material of (E) composition, can make the curable resin composition that obtains the cured article with less coefficient of linear expansion and tenacity excellent.In addition, can be provided in while shaping on the essence one side of the metal bases such as main lead frame take Cu the almost molding without warpage.
(D) silicoorganic compound of composition are the compound that its skeleton is formed by Si-O-Si key in fact, can use straight chain shape, ring-type, a chain, have the various silicoorganic compound such as compound of partial mesh topology.
In this case, as with the substituting group of skeleton bonding, can enumerate: the alkyl such as methyl, ethyl, propyl group, octyl group; The aryl such as phenyl, 2-phenylethyl, 2-phenyl propyl; The alkoxyl groups such as methoxyl group, oxyethyl group, isopropoxy; The groups such as hydroxyl.Wherein, aspect thermotolerance easily uprises, preferable methyl, phenyl, hydroxyl, methoxyl group, more preferably methyl, phenyl.
In addition, as containing the substituting group with SiH base with reactive carbon-to-carbon double bond, can enumerate: vinyl, allyl group, acryloxy, methacryloxy, acryloxy propyl group, methacryloxypropyl etc., wherein, reactivity good aspect, preferred vinyl.
As the example of (D) composition, it can be the material that can be expressed from the next.
R
n(CH
2=CH)
mSiO
(4-n-m)/2
More than 1000 silicoorganic compound of the molecular weight that (in formula, R is the group that is selected from hydroxyl, methyl or phenyl, and n, m are for meeting the number of 0≤n4,0<m≤4,0<n+m≤4) represents.
As the example of (D) composition, can enumerate: there is vinyl as the polydimethylsiloxane of terminal group or side chain radical, polydiphenylsiloxane, PSI or wherein random copolymers or the segmented copolymer etc. of 2 kinds or 3 kinds.As (D) composition, many kinds of substance can be mixed and uses.
Wherein, more easily obtaining aspect effect of the present invention, preferably end has the straight chain shape polysiloxane of vinyl, more preferably two ends have the straight chain shape polysiloxane of vinyl, further preferably two ends have straight chain shape polydimethyl-polydiphenylsiloxane or the straight chain shape PSI of vinyl, and being particularly preferably two ends, to have the straight chain shape polydimethyl-polydiphenylsiloxane of vinyl or straight chain shape PSI and phenyl be 10 % by mole of above siloxanes with respect to whole substituent amounts.
As the molecular weight of (D) composition, weight-average molecular weight (Mw) is more than 1,000, be preferably more than 2,000, more preferably more than 5,000, more preferably more than 10,000.When it was lower than 1,000 o'clock, there is the problem of toughness drop.In addition, as the molecular weight of (D) composition, be preferably below 1,000,000, more preferably below 100,000.Exceed at 1,000,000 o'clock, be difficult to obtain the consistency with (A) composition, (B) composition.
As the amount of (D) composition, (D) weight of composition with respect to (A) composition and (B) weight of the total of composition be preferably 30 % by weight above, more preferably 50 % by weight above, more preferably more than 80 % by weight.During lower than 30 % by weight, coefficient of linear expansion is difficult to reduce sometimes.
For the mixture ratio of (A) composition, (B) composition, (D) composition, only otherwise lose necessary intensity, just be not particularly limited, (B) number (Y) of the SiH base in composition with respect to (A) composition and (D) in composition with SiH base have the ratio of the number (X) of reactive carbon-to-carbon double bond preferable range under be limited to Y/X≤0.3, more preferably Y/X≤0.5, Y/X≤0.7 more preferably, in preferable range, be limited to Y/X≤3, more preferably Y/X≤2, Y/X≤1.5 more preferably.In the situation that departing from preferable range, sometimes can not obtain sufficient intensity, or become easy thermal degradation when.
((E) composition)
(E) composition is inorganic filling material.(E) composition has intensity or the hardness that improves the cured article obtaining or the effect that reduces linear expansion rate.
As the inorganic filling material of (E) composition, can use various inorganic filling materials, for example can enumerate: with quartz, aerosil, precipitation threshold silicon-dioxide, silicic anhydride, fused silica, crystallinity silicon-dioxide, the silica-based inorganic filling materials such as super-fine powder soft silica, aluminum oxide, zirconium white, titanium oxide, zinc oxide, silicon nitride, boron nitride, aluminium nitride, silicon carbide, glass fibre, sapphire whisker, carbon fiber, mica, blacklead, carbon black, graphite, diatomite, carclazyte, clay, talcum, aluminium hydroxide, calcium carbonate, magnesiumcarbonate, barium sulfate, barium titanate, potassium titanate, Calucium Silicate powder, inorganic microspheres, the inorganic filling materials such as silver powder are representative, epoxy systems etc. are used or/and the inorganic filling material proposing etc. conventionally as the packing material of current sealing material.As inorganic filling material, bring the viewpoint of infringement from being difficult for double conductor element, be preferably low radiation linear.
Inorganic filling material can suitably carry out surface treatment.As surface treatment, can enumerate: alkylation processing, trimethyl silyl processing, organosilicon processing, utilize processing that coupling agent carries out etc.
As the example of the coupling agent in this situation, can enumerate silane coupling agent.As silane coupling agent, there is reactive functional group and water-disintegrable silica-based compound as long as there is respectively at least 1 in molecule with organic group, be just not particularly limited.As thering is reactive group with organic group; from the viewpoint of operability; be preferably selected from least 1 functional group of epoxy group(ing), methacryloyl, acryl, isocyanate group, isocyanurate group, vinyl, carbamate groups; from the viewpoint of solidified nature and cementability, particularly preferably epoxy group(ing), methacryloyl, acryl.As water-disintegrable silica-based, from the viewpoint of operability, preferably alkoxysilyl, from the viewpoint of reactive, particularly preferably methoxy methyl silylation, (ethoxymethyl) silylation.
As preferred silane coupling agent, can example: 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-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.
In addition, can enumerate the method for adding inorganic filling material.For example can also enumerate: the alkoxide of the metals such as water-disintegrable to organoalkoxysilane, acyloxy silane, halogenated silane etc. silane monomer or oligopolymer, titanium, aluminium, acyl-oxygen compound, halogenide etc. are added in curable resin composition of the present invention, make it and react in curable resin composition or in the partial reaction thing of curable resin composition, in curable resin composition, generate the method for inorganic filling material.
In inorganic filling material as above, from being difficult to hinder curing reaction, the effect that reduces coefficient of linear expansion is large, the viewpoint that easily uprises with the cementability of lead frame, preferred silica-based inorganic filling material.And then, the physical property such as plasticity, electrical characteristic balance good aspect, preferred molten silicon-dioxide, aspect the package design that the thermal conductivity that can make encapsulation easily uprises, exothermicity is high, preferably crystallinity silicon-dioxide.Aspect exothermicity more easily uprises, preferential oxidation aluminium.In addition, aspect light extraction efficiency high at the luminous reflectance factor of potting resin, the photodiode that obtains easily uprises, preferential oxidation titanium.In addition, aspect intensity high in reinforced effects, encapsulation easily uprises, preferred glass fibers, potassium titanate, Calucium Silicate powder.
As median size or the size distribution of inorganic filling material, packing material take epoxies etc. as current sealing material and use or/and the material proposing as representative, can be not particularly limited to use various materials, under normally used median size (number average bead diameter), be limited to 0.1 μ m, easily become good from the viewpoint of mobility, be preferably 0.5 μ m, in normally used median size, be limited to 120 μ m, easily become good from the viewpoint of mobility, be preferably 60 μ m, more preferably 15 μ m.
For the specific surface area of inorganic filling material, use or/and the material proposing, as representative, can carry out various settings as the packing material of current sealing material take epoxy system etc.
As the shape of inorganic filling material, can use broken shape, sheet, the different shape such as spherical, bar-shaped.Long-width ratio also can be used various long-width ratios.Aspect the intensity of the cured article obtaining easily uprises, preferably long-width ratio is more than 10 material.In addition, from the viewpoint of the isotropy contraction of resin, compared with fibrous, preferred powder powder.Or, aspect the mobility while shaping in the time that height is filled also easily improves, preferably spherical material.
(E) composition is preferably spherical silicon dioxide.
These inorganic filling materials may be used alone, two or more kinds can also be used.
(E) amount of composition is not particularly limited, more than preferably the total amount of (E) composition accounts for 70 % by weight in curable resin composition entirety, more preferably more than 80 % by weight, further preferably more than 90 % by weight.During lower than 70 % by weight, intensity or hardness or reduce the effect of linear expansion rate are difficult to be improved.
As the order by merging of the inorganic filling material of (E) composition, can adopt the whole bag of tricks, the stability in storage of the intermediate raw material of curable resin composition easily become good aspect, preferably will in (A) composition, mix (C) composition and inorganic filling material and method that the mixture that obtains mixes with (B) composition.Adopt while mixing the method for (A) composition in the mixture that mixes (C) composition and/or inorganic filling material and obtaining in (B) composition, because moisture and/or inorganic filling material in (B) composition and environment under (C) composition exists and/or not have reactivity, therefore, sometimes rotten in the medium generation of storage.In addition, fully be obtained by mixing aspect stable molding as (A) composition, (B) composition, (C) composition of reacted constituent easily making, the mixture preferably (A) composition, (B) composition, (C) composition being obtained by mixing mixes with inorganic filling material.
As the scheme of inorganic filling material of mixing (E) composition, the various schemes that can use the institutes such as current epoxy resin to use and/or propose.For example can enumerate: the stirrers such as 2 roller mills or 3 roller mills, planetary churning deaerator, clarifixator, dispersator, planetary-type mixer, mould the melting mixing machines such as grinding machine etc.Wherein, though for high fill also can make inorganic filling material easily obtain sufficient dispersed aspect, preferably 3 roller mills, melting mixing machine.The mixing of inorganic filling material can be carried out at normal temperatures, also can heat and carry out.In addition, can under normal pressure, carry out, also can under decompression state, carry out.Even for high fill also can make inorganic filling material easily obtain sufficient dispersed aspect, preferably under heated condition, mix, improve inorganic filling material surface screening characteristics and easily obtain sufficient dispersed aspect, preferably under decompression state, mix.
((F) composition)
Curable resin composition of the present invention preferably contains white pigment ((F) composition).
(F) composition is white pigment, has the effect of the luminous reflectance factor that improves the cured article obtaining.
As (F) composition, can use various white pigments, for example can enumerate: titanium oxide, zinc oxide, magnesium oxide, weisspiessglanz, zirconium white, strontium oxide, niobium oxides, boron nitride, barium titanate, zinc sulphide, barium sulfate, magnesiumcarbonate, double glazing particle etc.Wherein, from the easiness of operation or the viewpoint of the property obtained, cost, preferential oxidation titanium or zinc oxide.
As the titanium oxide of (F) composition, can use various titanium oxide, can be Detitanium-ore-type, can be also rutile-type, aspect easily stablizing without photocatalysis, curable resin composition, be preferably rutile-type.
As the median size (number average bead diameter) of (F) composition, also can use various median sizes, easily uprise and curable resin composition flap becomes harder viewpoint from the luminous reflectance factor of the cured article that obtains, be preferably below 1.0 μ m, more preferably, below 0.30 μ m, most preferably be below 0.25 μ m.
On the other hand, the mobility of curable resin composition high aspect, more than being preferably 0.05 μ m, more preferably more than 0.1 μ m.Median size can be used laser diffraction and scattering formula size-grade distribution meter to measure.
As the manufacture method of the titanium oxide of (F) composition, can use the titanium oxide of manufacturing by any method such as sulfuric acid process, chlorine method.
(F) composition can be implemented surface treatment.
In the surface treatment of (F) composition, at coated at least a kind of being selected from mineral compound, organic compound in the surface of (F) composition.As mineral compound, for example can enumerate: aluminum compound, silicon compound, zirconium compounds, tin compound, titanium compound, antimony compounds etc., in addition, as organic compound, can enumerate: silicoorganic compound, higher fatty acid or its metal-salt, the organometallic compounds etc. such as polyvalent alcohol, alkanolamine or derivatives thereof, organo-siloxane.
In the case of the surperficial coated inorganic compound or organic compound of (F) composition, can use the known method of damp process or drying process, for example, in the time that titanium oxide dry type is pulverized, carry out when slurried or when case of wet attrition.In addition, can enumerate the whole bag of tricks such as liquid phase method, vapor phase process.
Wherein, good from the viewpoint of high, the heat-resisting photostabilization of luminous reflectance factor of the cured article that obtains, preferably process by organo-siloxane processing.In addition, even making the high good LED aspect that chien shih does not also reduce with light extraction efficiency for a long time of light extraction efficiency, also preferably contain the titanium oxide that has carried out organo-siloxane processing.
As the organo-siloxane treatment agent in this situation, can apply various materials.For example can enumerate: polydimethylsiloxane, PSI, polymethyl hydrogen siloxane or their multipolymer etc. are polysiloxane-based, hexamethyl cyclotrisiloxane, heptamethylcyclotetrasiloxane, 1,3,5, the cyclosiloxane classes such as 7-tetramethyl-ring tetrasiloxane, the chlorosilane classes such as trimethylchlorosilane, dimethyldichlorosilane(DMCS), METHYL TRICHLORO SILANE, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane etc. have the silicane 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 silicane of methacryloyl or acryl, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane etc. have the silicane of vinyl, γ mercaptopropyitrimethoxy silane, the hydrosulphonyl silane classes such as γ-sulfydryl propyl group methyl dimethoxysilane, γ aminopropyltriethoxy silane, γ-[two (beta-hydroxy ethyl)] aminopropyltriethoxywerene werene, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, γ-(beta-aminoethyl) aminopropyl dimethoxy-methyl silane, N-(trimethoxy-silylpropyl) quadrol, N-(dimethoxy-methyl silyl sec.-propyl) quadrol, N-β-(N-vinyl benzyl amino-ethyl)-gamma-amino propyl trimethoxy silicane etc. has amino silicane, isocyanic ester propyl trimethoxy silicane, isocyanic ester propyl-triethoxysilicane etc. have the silicane of isocyanate group, methyltrimethoxy silane, Union carbide A-162, hexyl Trimethoxy silane, hexyl triethoxyl silane, octyl group Trimethoxy silane, octyltri-ethoxysilane etc. have the silicane of alkyl, silane coupling agent or hexamethyldisiloxane, the hexamethyldisilazane etc. of the various silicane examples such as other silicane such as γ-r-chloropropyl trimethoxyl silane, γ-anilino propyl trimethoxy silicane.As these surface treatment agents, be preferably the not material of carbon-carbon double key, while containing carbon-to-carbon double bond, thermotolerance easily reduces.In addition, also can be used together organo-siloxane surface treatment in addition, also can process with Al, Zr, Zn etc.
In addition, can utilize mineral compound to carry out surface treatment.
For the surface treatment that utilizes mineral compound to carry out, be not particularly limited, can use the various surface treatments such as aluminum compound, silicon compound, zirconium compounds.In the situation of titanium oxide, the surface treatment that preferably utilizes aluminum compound to carry out.For titanium oxide, sometimes in order to improve the affinity of weather resistance, raising and medium or to carry out surface treatment for preventing the objects such as particle shape distortion with mineral compound, organic compound, can think by (F) composition being carried out to surface treatment with mineral compound, can improve with curable resin composition in the affinity of contained composition, (F) composition is improved with respect to the dispersiveness of curable resin composition, improve the intensity of cured article.
As surface-treated method, also can variety of methods, can example damp process, the whole bag of tricks such as drying process, liquid phase method, vapor phase process.
As the amount of (F) composition, be not particularly limited, but more than preferably the amount of (F) composition accounts for 10 % by weight in curable resin composition entirety, more preferably more than 15 % by weight, further preferably more than 20 % by weight.During lower than 10 % by weight, the luminous reflectance factor of the cured article sometimes obtaining reduces.
Be make the situation of white hardening resin composition but be applied to the black matrix etc. of display equipment in the case of using (F) composition, can use black curable resin composition.
As operable black pigment in this situation, can be any of mineral dye and pigment dyestuff, can use separately a kind or the pigment that is mixed with two or more.As mineral dye, for example can enumerate: carbon black, graphite, iron oxide black, titanium carbon, titanium are black, Manganse Dioxide, copper chromium Mn oxide.From putting forward high-strength viewpoint, preferably carbon black or titanium are black.And then from increasing the viewpoint of optical density (OD) and resistance value, more preferably titanium is black.In addition, also can use with resin etc. be coated surperficial carbon black or titanium black.Also can use nigrosine, Anthraquinones black pigment, perylene class black pigment etc.
In addition, as the black pigment of composite oxide of metal system, can also use copper-chromium-manganese system complex oxide black pigment, composite oxides black pigment take oxide compound, the oxide compound of cobalt and the oxide compound of aluminium of the oxide compound that contains copper, manganese as feature, for the ratio of copper, manganese, cobalt and aluminium that forms pigment, when the total of these metals is set as to 100 % by mole, copper is 5～30 % by mole, and manganese is 5～30 % by mole, cobalt is 15～40 % by mole, and aluminium is 25～50 % by mole.
((E) composition and (F) composition)
To (E) composition and (F) total amount of composition be not particularly limited, preferably (E) composition and (F) more than the amount of the total of composition accounts for 70 % by weight in curable resin composition entirety, more preferably more than 85 % by weight, particularly preferably more than 90 % by weight.In addition, be preferably below 97 % by weight, more preferably below 95 % by weight.During lower than 70 % by weight, intensity or hardness or reduce the effect of linear expansion rate are difficult to be improved.In addition, while exceeding 97 % by weight, plasticity reduces sometimes.
As the order by merging of (F) composition, can adopt the whole bag of tricks, optimal way is identical with (E) that illustrate.In addition, (F) composition and (E) composition can add simultaneously.
As the scheme of mixing (F) composition, can use the scheme identical with the scheme of mixing (E) composition.
((G) composition)
Curable resin composition of the present invention preferably contains metallic soap ((G) composition).(G) composition is to add in order to improve take the release property of curable resin composition as the formability of representative.
As (G) composition, can enumerate the various metallic soaps that use at present.At this so-called metallic soap, typically refer to the material of longer chain fatty acid and metal ion bonding gained, as long as in a part, have simultaneously nonpolarity or low polar portion based on lipid acid and based on the polar portion of the bonding part of metal, just can use.As longer chain fatty acid, can enumerate the saturated fatty acid of such as carbon number 1～18, unsaturated fatty acids, the aliphatic dicarboxylic acid etc. of carbon number 3～18.Wherein, from the viewpoint of easily obtain and industrial realization high, the preferably saturated fatty acid of carbon number 1～18, and then, high from the viewpoint of the effect of release property, the more preferably saturated fatty acid of carbon number 6～18.As metal ion, except basic metal, alkaline-earth metal, also can enumerate zinc, cobalt, aluminium, strontium etc.If more specifically illustrate metallic soap, can illustrate: lithium stearate, 12-hydroxy lithium stearate, lithium laurate, oleic acid lithium, 2 ethyl hexanoic acid lithium, sodium stearate, 12-hydroxyl sodium stearate, sodium laurate, sodium oleate, 2 ethyl hexanoic acid sodium, potassium stearate, 12-oxystearic acid potassium, potassium laurate, potassium oleate, 2 ethyl hexanoic acid potassium, Magnesium Stearate, 12-oxystearic acid magnesium, Magnesium monolaurate, magnesium oleate, 2 ethyl hexanoic acid magnesium, calcium stearate, 12-oxystearic acid calcium, calcium laurate, calcium oleate, 2 ethyl hexanoic acid calcium, barium stearate, 12-oxystearic acid barium, barium laurate, Zinic stearas, 12-oxystearic acid zinc, zinc laurate, zinc oleate, 2 ethyl hexanoic acid zinc, lead stearate, 12-oxystearic acid lead, cobalt stearate, aluminum stearate, manganese oleate, ricinolic acid barium etc.In these metallic soaps, from the viewpoint of easily obtaining, safe and industrial realization is high, preferably Metallic stearates class, particularly from the viewpoint of economy, is most preferably selected from a kind of above material in calcium stearate, Magnesium Stearate, Zinic stearas, aluminum stearate.
As the addition of this metallic soap, be not particularly limited, the lower limit of preferred amounts is 0.01 weight part (i.e. 0.01 % by weight), more preferably 0.025 weight part, 0.05 weight part more preferably with respect to overall 100 weight parts of curable resin composition, and the upper limit of preferred amounts is 5 weight parts (i.e. 5 % by weight), is preferably 4 weight parts with respect to overall 100 weight parts of curable resin composition.When addition is too much, cause sometimes the physical property of cured article to reduce, when very few, sometimes cannot obtain mold releasability.
(additive)
In curable resin composition of the present invention, can add various additives.
(solidifying retarding agent)
For improve curable resin composition of the present invention storage stability object or regulate reactive object of the hydrosilylation reactions in manufacturing processed, can use curing retarding agent.As curing retarding agent, can enumerate: the compound that contains aliphatics unsaturated link(age), organo phosphorous compounds, organosulfur compound, nitrogenous compound, tin based compound, organo-peroxide etc., can and use these materials.
As the compound that contains aliphatics unsaturated link(age), can example: the maleic acid ester classes such as propiolic alcohol, alkene-alkine compounds class, dimethyl maleate such as 3-hydroxy-3-methyl-ethyl acetylene, 3-hydroxyl-3-phenyl-ethyl acetylene, 1-ethynyl-1-hexalin etc.As organo phosphorous compounds, can example: three organic phosphine classes, two organic phosphine classes, organic phosphine acids, three organic phosphites etc.As organosulfur compound, can example: organosulfur alcohols, two organic sulfide classes, hydrogen sulfide, benzothiazole, thiazole, benzothiazyl disulfide etc.As nitrogenous compound, can example: ammonia, kiber alkyl amine, alkyl secondary amine, alkyl tert amine, aryl amine, urea, hydrazine etc.As tin based compound, can example: the sub-tin of two hydration halogenations, the sub-tin of carboxylic acid etc.As organo-peroxide, can example: di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, peroxidized t-butyl perbenzoate etc.
In these curing retarding agents,, raw material obtaining property good viewpoint good from blocking activity, preferably benzothiazole, thiazole, dimethyl maleate, 3-hydroxy-3-methyl-ethyl acetylene, 1-ethynyl-1-hexalin.
Solidify the addition of retarding agent and can carry out various settings, with respect to being limited to 10 under the preferred addition of the hydrosilylation catalysts 1mol using
-1mole, more preferably 1 mole, preferably addition on be limited to 10
3mole, more preferably 50 moles.
In addition, these curing retarding agents may be used alone, two or more kinds can also be used.
(cementability modifying agent)
In curable resin composition of the present invention, can also add cementability modifying agent.As cementability modifying agent, except normally used caking agent, for example can also enumerate: various coupling agents, epoxy compounds, resol, coumarone-indene resin, rosin ester resin, Terpene-phenolic resin, alpha-methyl styrene-vinyl toluene copolymer, poly-ethyl-methyl vinylbenzene, aromatic poly-isocyanate etc.
As coupling agent, can enumerate such as silane coupling agent, titanic acid ester is coupling agent etc.
Example or the preference of coupling agent are same as described above.
As the addition of coupling agent, can carry out various settings, with respect to being limited to 0.1 weight part, 0.5 weight part more preferably under the preferred addition of [(A) composition+(B) composition] 100 weight parts, preferably addition on be limited to 50 weight parts, 25 weight parts more preferably.When addition is few, sometimes can not show cementability improved effect, when addition is many, sometimes cured article physical property be brought to detrimentally affect.
As epoxy compounds, for example can enumerate: phenol aldehyde type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin, Bisphenol F diglycidylether, bisphenol A diglycidyl ether, 2,2 '-bis-(4-glycidoxy cyclohexyl) propane, 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate, vinyl cyclohexene dioxide, 2-(3,4-epoxycyclohexyl)-5,5-spiral shell-(3,4-epoxy cyclohexane)-1,3-bis-
alkane, two (3,4-epoxycyclohexyl) adipic acid ester, 1,2-cyclopropane dicarboxylic acid bisglycidyl ester, triglycidyl group isocyanuric acid ester, monoene propyl group diglycidyl isocyanuric acid ester, diallyl list glycidyl isocyanuric acid ester etc.
As the addition of epoxy compounds, can carry out various settings, with respect to being limited to 1 weight part, 3 weight parts more preferably under the preferred addition of [(A) composition+(B) composition] 100 weight parts, preferably addition on be limited to 50 weight parts, 25 weight parts more preferably.When addition is few, sometimes can not show cementability improved effect, when addition is many, sometimes cured article physical property be brought to detrimentally affect.
In addition, these coupling agents, silane coupling agent, epoxy compounds etc. may be used alone, two or more kinds can also be used.
In addition, in the present invention, in order to improve the effect of coupling agent or epoxy compounds, silanol condensation catalyst can be further used, cementability and/or stabilization can be improved.As this silanol condensation catalyst, be not particularly limited, preferably boron compound or/and aluminium compounds or/and titanium compound.
As the aluminium compounds that becomes silanol condensation catalyst, can illustrate: the aluminium alkoxide classes such as aluminum isopropylate, sec-butoxy aluminum-diisopropoxide, three aluminium secondary butylates; The aluminum chelate classes such as etheric acid aluminium triethyl diisopropyl ester (aluminum ethyl acetoacetate diisopropoxide), three (methyl aceto acetate) aluminium (aluminum tris (ethyl acetoacetate)), aluminum chelate M (length of schooling that becomes more meticulous, etheric acid aluminum alkyls diisopropyl ester are ground in river), aluminium tris(acetylacetonate), two (methyl aceto acetate) single acetyl acetone aluminium etc., from the viewpoint of operability, more preferably aluminum chelate class.
As the titanium compound that becomes silanol condensation catalyst, can example: the titanium chelate classes such as the four titan-alkoxide classes such as tetraisopropoxy titanium, four titanium butoxide, four acetyl acetone titaniums; There is the common titanate coupling agent of the residue such as oxyacetic acid or ethylene glycol.
As the borate compounds that becomes silanol condensation catalyst, can enumerate boric acid ester.As boric acid ester, can preferably use the material shown in following general formula (VII), (VIII).
[Chemical formula 1 5]
B(OR
1)
3(VII)
[Chemical formula 1 6]
B(OCOR
1)
3(vIII)
(in formula, R
1represent the organic group of carbon number 1～48.)
As the concrete example of boric acid ester, can preferably use: boric acid three-2-ethylhexyl, boric acid positive three (octadecyl) ester, boric acid three n-octyls, triphenyl borate, boric acid Sanya methyl esters, boric acid three (trimethyl silyl) ester, tri-n-butyl borate, the secondary butyl ester of boric acid three, boric acid three tert-butyl esters, triisopropyl borate ester, boric acid three n-propyls, boric acid triallyl, triethyl borate, trimethyl borate, methyl cellosolve boron.
These boric acid esters can only use a kind, also can be mixed with two or more.Mixing can be carried out in advance, in addition, also can in the time that cured article is made, mix.
In these boric acid esters, from the viewpoint of can easily obtain and industrial applicibility high, preferred boric acid trimethyl, triethyl borate, tri-n-butyl borate, wherein, more preferably trimethyl borate.
From the viewpoint of can suppress solidify time volatile, preferred boric acid positive three (octadecyl) ester, boric acid three n-octyls, triphenyl borate, boric acid Sanya methyl esters, boric acid three (trimethyl silyl) ester, tri-n-butyl borate, the secondary butyl ester of boric acid three, boric acid three tert-butyl esters, triisopropyl borate ester, boric acid three n-propyls, boric acid triallyl, methyl cellosolve boron, wherein, more preferably boric acid positive three (octadecyl) ester, boric acid three tert-butyl esters, triphenyl borate, tri-n-butyl borate.
Good from the viewpoint of suppressing volatility and operability, preferred boric acid tri-n-butyl, triisopropyl borate ester, boric acid three n-propyls, wherein, more preferably tri-n-butyl borate.
The low aspect of tint permanence from high temperature is considered, preferred boric acid trimethyl, triethyl borate, wherein, more preferably trimethyl borate.
Consumption while using silanol condensation catalyst can carry out various settings, with respect to coupling agent or/and the preferred addition of epoxy compounds 100 weight parts under be limited to 0.1 weight part, 1 weight part more preferably, preferably addition on be limited to 50 weight parts, 30 weight parts more preferably.When addition is few, sometimes can not show cementability improved effect, when addition is many, sometimes cured article physical property be brought to detrimentally affect.
In addition, these silanol condensation catalysts may be used alone, two or more kinds can also be used.
In addition, in the present invention, in order further to improve cementability improved effect, silanol source compound can be further used, cementability and/or stabilization can be improved.As this silanol source, for example can enumerate: the alkoxyl silicone alkanes such as the silanol compounds such as tri-phenyl-silane alcohol, Diphenylsilanediol, dimethoxydiphenylsilane, tetramethoxy-silicane, methyltrimethoxy silane etc.
Consumption while using silanol source compound can carry out various settings, with respect to coupling agent or/and the preferred addition of epoxy compounds 100 weight parts under be limited to 0.1 weight part, 1 weight part more preferably, preferably addition on be limited to 50 weight parts, 30 weight parts more preferably.When addition is few, sometimes can not show cementability improved effect, when addition is many, sometimes cured article physical property be brought to detrimentally affect.
In addition, these silanol source compounds may be used alone, two or more kinds can also be used.
In the present invention, in order to improve the effect of coupling agent or epoxy compounds, carboxylic-acid can be used or/and anhydrides can improve cementability and/or stabilization.As this carboxylic-acid, anhydrides, be not particularly limited, can be listed below material.
[Chemical formula 1 7]
Independent or the compound acid anhydrides of 2 ethyl hexanoic acid, hexahydrobenzoic acid, cyclohexane dicarboxylic acid, methylcyclohexane dicarboxylic acid, tetrahydrophthalic acid, methyl tetrahydrophthalic acid, methyl humic acids, norbornene dicarboxylic acids, hydrogenation methyl Na Dike acid, toxilic acid, acetylenedicarboxylic acid, lactic acid, oxysuccinic acid, citric acid, tartrate, phenylformic acid, hydroxy-benzoic acid, styracin, phthalic acid, trimellitic acid, Pyromellitic Acid, naphthoic acid, naphthalic acid and above-mentioned substance.
, aspect little in the possibility that there is hydrosilylation reactions, ooze out from cured article, to be difficult for the cured article that infringement obtains physical property, preferably contain with SiH base and there is reactive carbon-to-carbon double bond or/and in anhydrides at these carboxylic-acids.As preferred carboxylic-acid or/and anhydrides can be enumerated for example following substances:
[Chemical formula 1 8]
Independent or the compound acid anhydrides of tetrahydrophthalic acid, methyl tetrahydrophthalic acid and these materials etc.
Consumption when anhydrides uses carboxylic-acid or/and can carry out various settings, with respect to coupling agent or/and the preferred addition of epoxy compounds 100 weight parts under be limited to 0.1 weight part, 1 weight part more preferably, preferably addition on be limited to 50 weight parts, 10 weight parts more preferably.When addition is few, sometimes can not show cementability improved effect, when addition is many, sometimes cured article physical property be brought to detrimentally affect.
In addition, these carboxylic-acids or/and anhydrides may be used alone, two or more kinds can also be used.
In curable resin composition of the present invention, can use above-mentioned silane compound.Silane compound contributes to improve and the adaptation going between, and effectively prevents that moisture from immersing from the interface of encapsulation and lead-in wire.This silane compound of example, can enumerate: dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, aminomethyl phenyl dimethoxy silane, aminomethyl phenyl diethoxy silane etc., wherein, dimethyldimethoxysil,ne particularly preferably.
(cured article of heat-curing resin)
Heat reactive resin can will make the material pulverizing after resin solidification mix with particle state.Heat-curing resin is disperseed and while using, median size can be carried out various settings, under preferred median size, is limited to 10nm, in preferred median size, is limited to 10 μ m.Can have the distribution of particle system, can be single dispersion, also can have multiple peak value particle diameters, and, plasticity low from the viscosity of curable resin composition easily becomes good viewpoint, and the variation coefficient of particle diameter is preferably below 10%.
(thermoplastic resin)
For improving the objects such as characteristic, also can in curable resin composition of the present invention, add various thermoplastic resins.As thermoplastic resin, can use various thermoplastic resins, can example for example: such as, be the acrylic resin as representative such as resin take butyl polyacrylates such as random, the block of the homopolymer of the polymethylmethacrylate resinoids (OPTOREZ processed of Hitachi Chemical Co., Ltd. etc.) such as random, the block of the homopolymer of methyl methacrylate or methyl methacrylate and other monomer or graftomer, butyl acrylate or butyl acrylate and other monomer or graftomer, contain dihydroxyphenyl propane, 3,3,5-trimethylammonium cyclohexylidene bis-phenol etc. such as, as polycarbonate resins (APEC processed of Teijin Ltd etc.) such as the polycarbonate resins of monomer structure, the resin that norbornene derivative, vinyl monomer etc. is carried out to homopolymerization or copolymerization and obtain, the resin that norbornene derivative is carried out to ring opening metathesis polymerization and obtain, or the cycloolefin resinoid (APEL processed of for example Mitsui Chemicals, Inc such as its hydride, the Japan ZEON ZEONOR processed of Co., Ltd., ZEONEX, the ARTON processed of JSR Corp. etc.), alkene-the maleimides such as the multipolymer of ethene and maleimide are resin (the such as TI-PAS processed of Tosoh Co., Ltd. etc.), make dihydroxyphenyl propane, the glycols such as bisphenols or Diethylene Glycol and the terephthalic acids such as two (4-(2-hydroxyl-oxethyl) phenyl) fluorenes, the polyester based resins such as the polyester of the Phthalic acids such as m-phthalic acid or aliphatic dicarboxylic acid class polycondensation gained (the such as O-PET processed of Zhong Fang company etc.), polyethersulfone resin, polyarylate resin, polyvinyl acetal resin, polyvinyl resin, acrylic resin, polystyrene resin, polyamide resin, silicone resin, fluoro-resin etc., and natural rubber, the rubber-like resin of EPDM and so on, but be not limited to above-mentioned resin.
As thermoplastic resin, can in molecule, contain with SiH base and there is reactive carbon-to-carbon double bond or/and SiH base.The cured article obtaining easily become more tough and tensile aspect, preferably in molecule, in average 1 molecule, have that 1 is above and SiH base has reactive carbon-to-carbon double bond or/and SiH base.
As thermoplastic resin, can there is other crosslinkable groups.As the crosslinkable groups in this situation, can enumerate: epoxy group(ing), amino, free-radical polymerised unsaturated group, carboxyl, isocyanate group, hydroxyl, alkoxysilyl etc.Aspect the thermotolerance of the cured article obtaining easily uprises, preferably in average 1 molecule, there is more than 1 crosslinkable groups.
As the molecular weight of thermoplastic resin, be not particularly limited, with (A) composition and (B) consistency of composition easily become good aspect, preferred number average molecular weight is below 10000, more preferably below 5000.On the contrary, the cured article obtaining easily become tough and tensile aspect, preferred number average molecular weight is more than 10000, more preferably more than 100000.Also be not particularly limited for molecular weight distribution, viscosity, the plasticity of mixture easily become good aspect, molecular weight distribution is preferably below 3, more preferably below 2, more preferably below 1.5.
As the use level of thermoplastic resin, be not particularly limited, under preferable amount, be limited to 5 % by weight of curable resin composition entirety, 10 % by weight more preferably, in preferable amount, be limited to 50 % by weight of curable resin composition, 30 % by weight more preferably.The cured article that addition obtains when few easily becomes fragile, and addition thermotolerance of many times (Young's modulus under high temperature) is step-down easily.As thermoplastic resin, can use single material, also many kinds of substance can be used in combination.
Thermoplastic resin can be dissolved in (A) composition or/and (B) mix with uniform state in composition, also can pulverize with particle state and mix, and can also be dissolved in solvent, mixing etc. and becoming dispersion state.The cured article obtaining easily become more transparent aspect, be preferably dissolved in (A) composition or/and (B) mix with uniform state in composition.In this case, can make thermoplastic resin directly be dissolved in (A) composition or/and (B) in composition, also can use solvent etc. to mix equably, can also be thereafter except desolventizing forms as dispersion state is uniformly or/and admixture.
In the situation that thermoplastic resin is disperseed to use, median size can be carried out various settings, under preferred median size, is limited to 10nm, in preferred median size, is limited to 10 μ m.Can have the distribution of particle system, can be single dispersion, also can have multiple peak value particle diameters, and, plasticity low from the viscosity of curable resin composition easily becomes good viewpoint, and the variation coefficient of particle diameter is preferably below 10%.
(protective agent)
In curable resin composition of the present invention, can add protective agent.As protective agent, except the normally used protective agents such as hindered phenol system, also can enumerate citric acid or phosphoric acid, sulphur is protective agent etc.
Be protective agent as hindered phenol, can use the various materials take IRGANOX1010 as representative that can obtain from Ciba Specialty Chemicals company.Be protective agent as sulphur, can enumerate: the salt of thio-alcohol, mercaptan, to vulcanize carboxylic acid esters or comprise hindered phenol be sulfide-based sulfide-based, multiple sulfides, dithionic acid salt, Thiourea, group thiophosphate, sulfonium compound, thioaldehydes class, thiones, mercaptal class, mereaptol class, single sulfo-acids, polythio acids, thioamide analog, sulfoxide type etc.
In addition, these protective agents may be used alone, two or more kinds can also be used.
(free radical inhibitors)
In curable resin composition of the present invention, can add free radical inhibitors.As free radical inhibitors, for example can enumerate: 2,6-di-t-butyl-3-methylphenol (BHT), 2,2 '-methylene radical-bis-(4-methyl-6-tert-butylphenol), four (methylene radical-3 (3,5-di-tert-butyl-hydroxy phenyl) propionic ester) the phenols free radical inhibitors such as methane or Phenyl beta naphthylamine, alpha-naphthylamine, N, N '-sec-butyl-Ursol D, phenothiazine, N, the amine such as N '-phenylbenzene-Ursol D are free radical inhibitors etc.In addition, these free radical inhibitors may be used alone, two or more kinds can also be used.
(UV light absorber)
In curable resin composition of the present invention, can add UV light absorber.As UV light absorber, for example can enumerate: 2 (2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) benzotriazole, two (2,2,6,6-tetramethyl--4-piperidines) sebate etc.
In addition, these UV light absorber may be used alone, two or more kinds can also be used.
(solvent)
Curable resin composition of the present invention also can be dissolved in solvent and use.Example particularly operable solvent is not particularly limited, if can preferably be used: the hydrocarbon system solvents such as benzene, toluene, hexane, heptane; The ether series solvents such as tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxs, DOX, Anaesthetie Ether; The ketone series solvents such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Chloroform, methylene dichloride, 1, the halogen series solvents such as 2-ethylene dichloride.
As solvent, preferably toluene, tetrahydrofuran (THF), DOX, chloroform.
The quantity of solvent using can suitably be set, and with respect to being limited to 0.1mL under the preferable amount of used curable resin composition 1g, is limited to 10mL in preferable amount.When consumption is few, be difficult to obtain the effect of the use solvents such as lowering viscousity, in addition, when consumption is many, dissolvent residual, in material, easily forms the problems such as thermal crack, in addition, also unfavorable aspect cost, and industrial utilization is worth and reduces.
These solvents can use separately, also can use with the form of mixed solvent of more than two kinds.
(for the additive of photodiode)
And then, in curable resin composition of the present invention, can add as required various for improving the additive of photodiode characteristic.As additive, for example can enumerate: the yttrium aluminum garnet with cerium activation that absorbs the light of self-emission device and send long wavelength's more fluorescence is the tinting materials such as the fluor such as fluor or the bluing agent that absorbs specific wavelength, for making the thermal conductivity packing materials such as the metal nitrides such as the metal oxide such as diffusion material, aluminosilicate, aluminium nitride, boron nitride such as titanium oxide, aluminum oxide, melamine resin, CTU guanamine resin, benzoguanamine resin etc. of light diffusion.Can contain equably for the additive that improves photodiode characteristic, also can give gradient to content and contain.
(releasing agent)
Release property while shaping in order to improve can add various releasing agents in curable resin composition of the present invention.
As releasing agent, can enumerate (G) composition, the wax class etc. that have illustrated.
As wax class, can example: natural wax, synthetic wax, oxidation or non-oxide polyolefine, polyethylene wax etc.
In addition, even in the situation that not adding releasing agent and can obtaining sufficient release property yet, preferably do not use releasing agent.
(other additive)
In curable resin composition of the present invention, not damaging in the scope of object of the present invention and effect, can add in addition tinting material, fire retardant, flame retardant, tensio-active agent, defoamer, emulsifying agent, flow agent, antishrinking agent, the ion trap agent of antimony-bismuth etc., thixotropy imparting agent, binding property imparting agent, preserve and stablize modifying agent, anti-ozone degradation, photostabilizer, thickening material, softening agent, reactive diluent, antioxidant, thermally-stabilised agent, electroconductibility imparting agent, antistatic agent, radioactive rays screener, nucleator, Phosphorus peroxide decomposer, lubricant, pigment, metal passivator, thermal conductivity imparting agent, physical property conditioning agent etc.
(B stage)
Curable resin composition of the present invention can directly use the title complexs such as each composition and additive, also can be waited and be made to use after partial reaction (B stage) by heating.By carrying out the B stage, can adjusting viscosity, also can regulate transmission plasticity.
In addition, also there is the effect of further inhibition cure shrinkage.
(curable resin composition proterties)
As curable resin composition of the present invention, as mentioned above, can use the material of various combinations, the plasticity being shaped by transmission etc. good aspect, as curable resin composition, preferably at the temperature below 150 ℃, there is mobility.
For the solidified nature of curable resin composition, can at random set, can shorten aspect forming period, the gelation time at 120 ℃ is preferably in 120 seconds, in more preferably 60 seconds.In addition, the gelation time at 150 ℃ be preferably in 60 seconds, in more preferably 30 seconds.In addition, the gelation time at 100 ℃ be preferably in 180 seconds, in more preferably 120 seconds.
Gelation time in this situation can as described belowly detect.On the hot plate that is adjusted to design temperature, place the aluminium foil of thickness 50 μ m, place curable resin composition 100mg thereon, measure the time to gelation, be set as gelation time.
In the manufacturing process of use curable resin composition, aspect being difficult for occurring to produce space in curable resin composition and causing the viewpoint of the problem in operation because discharge gas from curable resin composition, the weight in solidifying reduce be preferably 5 % by weight following, more preferably 3 % by weight following, more preferably below 1%.
Loss of weight in solidifying can as described belowly detect.Can use thermogravimetric analysis device, 10mg sealing agent is warming up to 150 ℃ with the heat-up rate of 10 ℃/min from room temperature, with the form of the ratio of the relative initial stage weight of weight that reduces and obtain.
In addition, in the situation that using as electronic material etc., aspect the difficult problem that organosilicon pollution occurs, the content of the Si atom in the volatile component in this situation is preferably below 1%.
(purposes of curable resin composition)
Curable resin composition of the present invention as described later can be for the manufacture of semi-conductive encapsulation.
(curing)
For curable resin composition of the present invention, be pre-mixed, make part or all the SiH base in composition and there is reactive carbon-to-carbon double bond with SiH base to carry out hydrosilylation reactions, can make thus it solidify.
Requirement that can the each composition of disposable mixing and make its reaction, also can adopt: mixing a part makes after its reaction, mixes residual content, further makes the method for its reaction; After mixing as mentioned above, the processing such as only make to form after a part of functional group reactions (B stage) in composition, further make its curing method.According to these methods, in the time being shaped, easily carry out viscosity adjustment.
(cured article proterties)
From the good viewpoint of thermotolerance, curable resin composition is solidified and the Tg of the cured article that obtains be preferably 100 ℃ above, more preferably more than 150 ℃.In this case, Tg can as described belowly detect.By using the corner post shape test film of 3mm × 5mm × 30mm, at stretch mode, the peak temperature of measuring the tan δ of the Measurement of Dynamic Viscoelasticity (use IT Meter & Controls, Inc. DVA-200 processed) that frequency 10Hz, strain 0.1%, quiet/power measure than 1.5, under the condition of 5 ℃/min of heat-up rates is set as Tg.
In addition, from being difficult for occurring lead frame etc. aspect the problems such as ion migration and reliability uprise, from the extraction ion content of cured article preferably lower than 10ppm, more preferably less than 5ppm, further preferably lower than 1ppm.
In this case, extraction ion content can as described belowly detect.The cured article 1g of cutting is put into teflon container made (teflon is registered trademark) together with ultrapure water 50ml and carry out airtightly, under 121 ℃, 2 normal atmosphere, the condition of 20 hours, process.Utilize ICP mass analysis (using Yokogawa Analytical Systems Inc. HP-4500 processed) to analyze the extraction liquid obtaining, the value of the content of the Na obtaining and K is scaled to the concentration in used cured article and obtains.On the other hand, utilize ion chromatography (using Nippon Dionex K.K. DX-500 processed, chromatographic column: AS12-SC) to analyze identical extraction liquid, the value of the content of the Cl obtaining and Br is scaled to the concentration in used cured article and obtains.Content in the cured article of the Na obtaining as mentioned above, K, Cl, Br is added up to and is set as extracting ion content.
As the coefficient of linear expansion of cured article, be not particularly limited, with the cementability of the metal such as lead frame or pottery etc. easily become good aspect, from the average coefficient of linear expansion of 23 ℃ to 150 ℃ be preferably below 30ppm, more preferably below 20ppm, more preferably below 10ppm.
In addition, the surperficial reflection of light rate to wavelength 480nm that curable resin composition of the present invention solidifies the molding forming is preferably more than 80%.
In addition, the luminous reflectance factor R of the 460nm after preferred consolidation and 480nm is more than 80%, and the conservation rate (luminous reflectance factor × 100 at the luminous reflectance factor/initial stage after oven test) of the luminous reflectance factor after the oven test of 180 ℃, 24 hours is more than 90%.
The as described below detection of luminous reflectance factor of cured article.Use small light splitting colour-difference meter (the Japanese electricity Se VSS400 processed of Industrial Co., Ltd) to measure the luminous reflectance factor of wavelength 400nm～700nm (interval 20nm).At this, the measured value of each wavelength adopts any 4 places of encapsulation upper surface (to measure area
the mean value of measured value.
Aspect the light extraction efficiency of photodiode easily uprises, in the wavelength region may of 420～700nm, luminous reflectance factor is preferably more than 75%, more preferably more than 80%.
In addition, for example, luminous reflectance factor after oven test (, heating the test of 24 hours in the baking oven of 180 ℃) utilizes following calculating formula to obtain with respect to the conservation rate of the luminous reflectance factor at initial stage." luminous reflectance factor at initial stage " refers to the luminous reflectance factor before oven test.
Conservation rate (%)=(luminous reflectance factor after oven test)/(luminous reflectance factor at initial stage) × 100
In the time using as electronic material reliability high aspect, conservation rate is preferably more than 80%, more preferably more than 85%, more preferably more than 90%.
In addition, as curable resin composition of the present invention is solidified and the molding that obtains, the reflection of light rate to wavelength 480nm on surface is preferably more than 80%, more preferably more than 90%, more preferably more than 95%, further more preferably more than 97%, be particularly preferably more than 99%.
In addition, for example, from demonstrate the viewpoint of good resistance to bend(ing) by the curable resin composition the present invention being carried out to molding that transfer die shaping obtains, the flexural strength of dull and stereotyped (molding) is preferably 50N/mm
245N/mm more preferably below,
240N/mm more preferably below,
2below.Flexural strength exceedes 50N/mm
2time, sometimes can not obtain sufficient flexibility.
In addition, similarly in the case of obtaining molding by the curable resin composition in the present invention being carried out to transfer die shaping, even if also can not cause the viewpoint of the unfavorable condition (below this characteristic being called to continuous molding) such as cohesion destruction of molding from being repeatedly shaped continuously, dull and stereotyped flexural strength is preferably at 20～50N/mm
2scope in, more preferably at 23～45N/mm
2scope in, further preferably at 25～40mm
2scope in.Flexural strength is lower than 20N/mm
2time, likely continuous molding variation, exceedes 50N/mm
2time, sometimes damage the flexibility of molding, resistance to bend(ing) reduces.
Dull and stereotyped flexural strength is as described below measures for these.Cut test film from the flat board of making, so that the length of test film is below the above 80mm of 50mm, width is 7mm～8mm left and right, 2 relative limits are parallel, with the Physical Property Analysis instrument processed TA.plus of Stable Micro Systems company, use the pressurization wedge being formed by the right-angle triangle of the glass system of the fillet of width 10mm, the speed applied load to the central authorities of test film with 2.0mm/sec, load (fracture load by bending N) while being fractureed by test film, utilizes following formula to calculate flexural strength σ
b(N/mm
2).
σ
b=M/I×h/2=(wl/4)/(bh
3/12)×h/2
At this, w is that fracture load by bending (N), l are that length of support is that member section lengthwise (mm), b are that member section is grown crosswise (mm) from (mm), h, and M is bending moment, and I is 2 times, cross section moment.
(curable resin composition flap)
By containing, (A)～(F) curable resin composition of composition forms flap of the present invention.
In addition, curable resin composition flap is characterised in that, (A) composition and (B) at least one party of composition be that the viscosity of 23 ℃ is the liquid below 50Pa second, (E) composition is with (F) content of the total of composition is (following, be sometimes referred to as filling ratio) be 70～95 % by weight, the particle below 12 μ m (E) composition and (F) in the total of composition shared ratio be more than 40 volume %.At this, (E) composition and (F) composition be powder.
(A) composition and (B) at least one party of composition be that the viscosity of 23 ℃ is the liquid below 50Pa second.When the viscosity of 23 ℃ exceedes 50Pa second, the problem that exists the operability while preparing composition to reduce.Viscosity be preferably 40Pa second following, below more preferably 30Pa second.
For this curable resin composition flap, by at high temperature (A) composition and (B) component viscosity reduce and curable resin composition entirety can flow, while further continuing heating, curing reaction carries out, and can be shaped as desired shape.
As manufacturing process, be not particularly limited, can adopt the manufacturing process such as transmission shaping or compression molding of the shaping that is generally used for curable resin composition.Adopting these manufacturing process in the situation that, while being pasty state or argillaceous as the curable resin composition of raw material, can not keep fixing shape, there is adhesion mutually, integrated, distortion, therefore, measure, to carry, be supplied to forming mill very difficult.On the other hand, when curable resin composition is flap shape, measure, carry, be supplied to forming mill and become easily, also becoming can automatization, and productivity increases substantially.Refer at this so-called flap the shape that at room temperature keeps fixing, there is no in fact ageing change of shape, and also do not adhere mutually or integrated solid in the time being in contact with one another.
The shape of flap of the present invention is not particularly limited, and comprises cylindric, corner post shape, the shape such as discoid, spherical, preferably transmits in being shaped common cylindric.
(E) composition and (F) content of the total of composition in flap of the present invention, account for 70～95 % by weight.More than total content is preferably 72 % by weight, more preferably more than 75 % by weight.In addition, be preferably below 94 % by weight, more preferably below 90 % by weight.
For (E) composition in filling ratio and (F) distribution of composition, be not particularly limited, can free setting.
Filling ratio is during lower than 70 % by weight, and it is large that the coefficient of thermal expansion of the cured article obtaining becomes, and the dimensional change of molding becomes problem, or exists curable resin composition to become hard pasty state or argillaceous and can not form the problem of flap.When filling ratio exceedes 95 % by weight, deposit that viscosity at high temperature becomes too high and plasticity reduces or the flap that obtains became crisp problem.
In curable resin composition of the present invention, (A) composition and (B) when at least one party of composition is liquid at normal temperatures, in the situation that filling ratio is low, easily becomes pasty state or argillaceous.Now, although can not form flap, the plasticity of depositing at high temperature easily becomes good tendency.On the other hand, in the situation that filling ratio is high, because mobile composition is few, therefore, easily become shred or powdery.It can press solidly slabbing thing shape by compressing, but deposits illiquidity at high temperature and tendency that plasticity easily reduces.Up to now, be difficult to only take into account sheet materialization and plasticity by increasing simply filling ratio.
But, in curable resin composition of the present invention, find by the particle below 12 μ m, more than shared ratio is set as 40 volume % in the total of (E) composition of powder and (F) composition, can take into account sheet materialization and plasticity.In addition, the particle below 12 μ m is more than at (E) composition and (F) shared ratio is preferably 60 % by weight in the total of composition.
As its reason, consider to be presumed as follows.Consider that in the mixed system of liquid and particle the surface of liquid component coating particles thinks that the unnecessary liquid component of coated all particles contributes to distortion.Therefore, even if consider that filling ratio is identical, the more total surface areas of ratio of small-particle are larger, and coated needed liquid component increases, and are difficult to distortion thereby become.Can think, because the viscosity with temperature of liquid raises and significantly reduces, therefore, the at high temperature variation of mobility is little with respect to the ratio of small-particle, and viscosity is high at low temperatures, therefore, can not be mobile as pasty state or argillaceous when small-particle is many, and become shred or powdery.
In other words,, by increasing the ratio of the small-particle in particle, can the mobility under the high temperature that maintains curable resin composition, make the state under normal temperature firm.Can not expect this situation by using under normal temperature the patent documentation 3 of only having recorded median size for the size-grade distribution of the epoxy resin of solid or the document of silicon-type resin (TOHKEMY 2008-112977 communique, TOHKEMY 2009-155415 communique) or not mentioned particle.
Except controlling size distribution, in order to obtain the good flap of operability, preferably separately use or and with use can effectively keep by the liquid resin of (A)～(D) composition formation, for example Porous weighting agent or there is the filler of oil absorbency.As this Porous weighting agent or there is the shape of the filler of oil absorbency, be not particularly limited, for example can use: spherical shape, broken shape, discoid, bar-shaped, fibrous etc.Mobility in mould while considering transfer molding, is preferably spherical shape, broken shape.
Particularly, can enumerate: spherical silicon dioxide, broken silicon-dioxide, aluminum oxide, magnesium oxide, weisspiessglanz, titanium oxide, zirconium white, aluminium hydroxide, magnesium hydroxide, barium sulfate, magnesiumcarbonate, barium carbonate, zeolite etc., these materials can use separately, also can be used together.From the viewpoint of thermal conductivity, reflective character, formability, preferably silicon-dioxide, aluminum oxide or their mixture.
In addition, for above-mentioned Porous weighting agent or have the filler of oil absorbency, physical property or chemical hydrophilicity-imparting treatment or hydrophobization processing can be carried out in its surface.Preferably effects on surface carries out hydrophobization processing, preferably the material of oil number (specified amount take JIS K5101 as standard) more than 50ml/100g.
In addition, for above-mentioned Porous weighting agent or there is the apparent density of the filler of oil absorbency, be not particularly limited, be preferably 0.4g/cm
3above, 0.4～2.0g/cm more preferably
3.Be explained, apparent density refers to the density in density that the starting material of filler considering Porous weighting agent or have oil absorbency are shared and the shared space (being pore volume) of minute aperture.This apparent density is lower than 0.4g/cm
3time, the physical strength of filler particles is little, in the time producing the melting mixing of shearing force as mixing roll mill etc., has the destroyed anxiety of particle.On the other hand, apparent density exceedes 2.0g/cm
3time, the tendency of easily adhering to curable resin composition at the die surface of mortar mould and pestle mould while there is flap moulding.
In addition, above-mentioned Porous weighting agent or the median size with the filler of oil absorbency are preferably 0.1～100 μ m, while considering with the packing efficiency of white pigment, and the more preferably scope of 1～10 μ m.When median size is greater than 100 μ m or is less than 0.1 μ m, the tendency of the mobility variation of curable resin composition while there is the melting while carrying out transfer molding.
In addition, above-mentioned Porous weighting agent or the specific surface area with the filler of oil absorbency are preferably 100～1000m
2/ g, 300～700m more preferably
2/ g.Specific surface area is less than 100m
2when/g, exist the oil number of the resin that brought by weighting agent to diminish, resin is easily attached to the tendency on pestle mould when flap moulding, specific surface area is greater than 1000m
2when/g, the tendency of the mobility variation of curable resin composition while there is the melting while carrying out transfer molding.
In addition, above-mentioned Porous weighting agent or the content with the filler of oil absorbency are not particularly limited, take (E) inorganic filling material and (F) total amount of white pigment as benchmark, be preferably the scope of 0.1 volume %～20 volume %.While considering the formability of resin combination when melting, more preferably 1 volume %～5 volume %.When this content is less than 0.1 volume %, a part for curable resin composition is easily attached to the forming mould surface of mortar mould and pestle mould, when this content is greater than 20 volume %, and the tendency that while there is the melting while carrying out transfer molding, the mobility of resin combination reduces.
(semi-conductive encapsulation)
Semi-conductive encapsulation of the present invention forms curable resin composition of the present invention and obtain, for example, be shaped to obtain by transmission.
Semi-conductive encapsulation can be that curable resin composition and metal are carried out integrally formed and obtained.For example can enumerate: utilize transfer die to carry out integrally formed and the member obtaining or the member forming at the one side shaping resin of metal in fact curable resin composition and lead frame.
So-called semi-conductive encapsulation in the present invention, refers in order to support fixing or/and protection semiconductor element or/and the outside member that takes out electrode etc. and arrange.Can be not directly the situation lower support fixed outer of coated semiconductor element extract the member of electrode etc. or form around the semiconductor element as the reverberator of photodiode or the member of bottom surface.
As the semiconductor element in this situation, can enumerate various semiconductor elements.For example, except the elements such as the unicircuit such as IC, LSI, transistor, diode, photodiode, can also enumerate the photo detectors such as CCD etc.
Be not particularly limited for shape, have in fact the shape at the one side shaping resin of metal (MAP type) in semi-conductive encapsulation, especially easily obtain effect of the present invention.
Be explained, in described above semi-conductive encapsulation of the present invention directly in the situation of coated semiconductor element etc., also can further use sealing agent to seal, for example, can use the sealing resins such as the epoxy resin, silicone resin, acrylic resin, urea resin, imide resin of current use.In addition, also can use as in TOHKEMY 2002-80733, TOHKEMY 2002-88244, propose, comprise to contain and in 1 molecule, there are at least 2 sealing agents that there is the aliphatics series organic compound of reactive carbon-to-carbon double bond with SiH base, there is the compound of at least 2 SiH bases and the curable resin composition of hydrosilylation catalysts in 1 molecule, aspect high with the cementability of potting resin and the high remarkable aspect of effect of transparency photostabilization high and encapsulation of the present invention, preferably use sealing agent.On the other hand, also can not use resin sealing, and seal by hermetically sealing with coverings such as glass.
In addition, in situation of photodiode or photo detector etc., also can further apply lens, also sealing agent can be configured as to lens shape and make it have lens function.
(manufacturing process)
As the manufacturing process of so-called semiconductor packages in the present invention, can make in all sorts of ways.Can use such as injection forming, transmission shaping, RIM shaping, casting forming, press molding, compression molding etc. to be generally used for the various manufacturing process of the heat-curing resin such as thermoplastic resin or epoxy resin, silicone resin.Wherein, aspect, plasticity short in forming period is good, preferably transmits and be shaped.
Molding condition also can be set arbitrarily, for example, about forming temperature, can be arbitrary temp, but at quick solidifying, forming period short and plasticity easily become good aspect, be preferably 100 ℃ of above, more preferably 120 ℃ of above, further preferred 150 ℃ of above temperature.After being shaped by the whole bag of tricks as above, carry out arbitrarily as required after fixing.Carrying out after fixing easily makes thermotolerance uprise.
Shaping can be carried out under fixed temperature, also multistage or continuously transformation temperature as required.Easily obtaining without aspect the even cured article of distortion, compared with carrying out with under fixed temperature, preferably on one side multistage or make continuously temperature rise react on one side.In addition, shortening aspect forming period, preferably under fixed temperature, carry out.
Also can carry out various settings set time, easily obtaining, without aspect the even cured article of distortion, and carrying out reacting phase ratio between high temperature, short time, preferably react for a long time than under lower temperature.On the contrary, can shorten aspect forming period, preferably at high temperature the short period of time reacts.
Pressure when shaping also can carry out various settings as required, can under normal pressure, high pressure or decompression state, form.Suppressing the generation in space, improve fillibility or easily remove according to circumstances aspect the volatile component producing, preferably under decompression state, be cured.Aspect can preventing that molding from cracking, preferably under pressurized state, be cured.
(purposes of photodiode)
Semiconductor device of the present invention is manufactured with semi-conductive encapsulation of the present invention.Semiconductor device of the present invention can be for current known various uses.Particularly, can enumerate: the LSI such as logical unit, storer, various sensor, be subject to luminaire etc.In addition, photodiode of the present invention is manufactured with semi-conductive encapsulation of the present invention.Semi-conductor is in the situation of photodiode, also can be for current known various uses.Particularly, for example can enumerate: the light source of the backlight of liquid crystal indicator etc., illumination, sensor light source, vehicle instrument light source, signal lamp, exhibited light, display unit, planar twinkler, indicating meter, decoration, various lamps etc.
(warpage)
When the one side that curable resin composition of the present invention is formed in to the effective lead frame of light-emitting diodes is made encapsulation, the warpage of preferred package is ± below 1.0mm.
Warpage in this situation can be based on recording in JIS C6481 the measuring method of maximum warpage measure.That is, semiconductor package is contained in to central vertical on one side and hangs, put abreast ruler on this limit.Ruler is placed on the concave surface of semiconductor packages, measures the largest interval of substrate surface of ruler and semiconductor packages to the unit of 1.0mm with metal ruler processed.In the time that the concave surface of semiconductor packages is formed with resin, the largest interval of resin face of measuring ruler and forming in semiconductor packages with metal ruler processed, to the unit of 1.0mm, is rounded to the value that is deducted the thickness gained of resin by this value the unit of 1.0mm.Other limit is also measured successively, largest interval is set as to warpage.Be explained, make by the method shown in embodiment (manufacturing process of MAP product) for the semiconductor packages of measuring warpage.
Embodiment
Below, embodiments of the invention and comparative example are shown, but the present invention is not limited by following content.
(synthesis example 1)
In 500mL four-hole boiling flask, put into toluene 200g, 1,3,5,7-tetramethyl-ring tetrasiloxane 50g, after gas phase portion is carried out to nitrogen replacement, heats, stirs 105 ℃ of internal temperatures.With the mixed solution that drips xylene solution (containing 3wt% in the platinum) 0.0162g of diallyl list glycidyl isocyanuric acid ester 11.0g, toluene 11.0g and vinylsiloxane-platinum complex for 30 minutes.Finish, 6 hours, to pass through from dripping
1h-NMR confirms that allylic reactivity is more than 95%, reacts by cooling end.Decompression is heated up in a steamer unreacted 1,3,5, and 7-tetramethyl-ring tetrasiloxane and toluene, obtain water white liquid.Pass through
1h-NMR measures known, and this liquid is that a part of SiH base of 1,3,5,7-tetramethyl-ring tetrasiloxane reacts with diallyl list glycidyl isocyanuric acid ester and the material with following structure that obtains.Equivalent conversion while confirming basis take reference material as ethylene dibromide in addition has SiH base 7.5mmol/g.
[Chemical formula 1 9]
(synthesis example 2)
Whipping appts, dropping funnel, prolong are set in the four-hole boiling flask of 5L.In this flask, put into toluene 1800g, 1,3,5,7-tetramethyl-ring tetrasiloxane 1440g heats, stirs in the oil bath of 120 ℃.With the mixed solution that drips xylene solution (containing 3wt% in the platinum) 1.44ml of cyanacrylate 200g, toluene 200g and vinylsiloxane-platinum complex for 50 minutes.The solution obtaining is directly carried out after 6 hours heating, stirring, and decompression is heated up in a steamer unreacted 1,3,5,7-tetramethyl-ring tetrasiloxane and toluene.Pass through
1h-NMR measures known, and this liquid is that a part of SiH base of 1,3,5,7-tetramethyl-ring tetrasiloxane reacts with cyanacrylate and the material with following structure that obtains.
[Chemical formula 2 0]
(synthesis example 3)
In 2L autoclave, put into toluene 720g, 1,3,5,7-tetramethyl-ring tetrasiloxane 240g, with after nitrogen replacement, heats gas phase portion, stir 50 ℃ of jacket temperature.With the mixed solution that drips xylene solution (containing 3wt% in the platinum) 0.049g of glycidyl allyl ether 171g, toluene 171g and vinylsiloxane-platinum complex for 90 minutes.After dropping finishes, jacket temperature is warming up to 60 ℃, reacts 40 minutes, pass through
1h-NMR confirms that allylic reactivity is more than 95%.After dripping the mixed solution of cyanacrylate 17g, toluene 17g, jacket temperature is warming up to 105 ℃, with the mixed solution that drips xylene solution (containing 3wt% in the platinum) 0.033g of cyanacrylate 66g, toluene 66g and vinylsiloxane-platinum complex for 30 minutes.Finish, 4 hours, to pass through from dripping
1h-NMR confirms that allylic reactivity is more than 95%, reacts by cooling end.The unreacted rate of 1,3,5,7-tetramethyl-ring tetrasiloxane is 0.8%.Reduce pressure and heat up in a steamer until unreacted 1,3,5, the by product (the interior transfer thing (cis body and trans body) of the vinyl of glycidyl allyl ether) of 7-tetramethyl-ring tetrasiloxane, toluene and glycidyl allyl ether adds up to 5, below 000ppm, obtain water white liquid.Pass through
1h-NMR measures known, and this liquid is that a part of SiH base of 1,3,5,7-tetramethyl-ring tetrasiloxane reacts with glycidyl allyl ether and cyanacrylate and the material that obtains, on average has following structure.
[Chemical formula 2 1]
(a+b=3、c+d=3、e+f=3、a+c+e=3.5、b+d+f=5.5)
(coordinating example 1～3, coordinating example A, B)
Coordinate each composition according to the content of table 1, prepare composition 1～3 and composition A, B.
[table 1]
(embodiment 1～9 and comparative example 1～3)
According to the use level of each composition of recording in table 2, so that being about the mode of 100g, its total takes, prepare curable resin composition of the present invention according to following main points.
In the container of cup-shaped, take separately the composition 1～3 recorded in the table 1 of preparation, A, B and (D) mixed solution of composition, add bit by bit (G) composition of being pre-mixed, (F) composition (or carbon black) and (E) mixed powder of composition, carry out mixing with plastics scraper.The curable resin composition obtaining is moistening slightly powdery, if after repeating to roll with the instrument of pole shape, folding, the operation of calendering again, humidification and become moistening shred uniformly lentamente.Wherein, the material that amount of filler is many, the ratio material how of micro mist are until be still finally (moistening slightly) powder shaped.Spherical silicon dioxide uses following substances.
MSR-3500, MSR-2212TN, MSR-SF650, MSR-SF630, MSR-04 use the gloomy system of Co., Ltd. dragon, and Admafine SO-2C uses the Admatechs of Co., Ltd. system.
The zinc oxide (ZnO-1) of white pigment uses Sakai KCC system, and titanium oxide (PC-3) uses Shi Yuan Industrial Co., Ltd system.Be explained, PC-3 is for having carried out surface-treated titanium oxide with Al, Si and organism.
Carbon black uses the dimethyl polysiloxane surface treatment acetylene black (name of product: SI06-2denka black is granular) of Daito Kasei Kogyo Co., Ltd's system.
The calcium stearate of releasing agent uses Sakai KCC system.
(sheet materialization)
Use the flap fabrication tool being formed by metal pestle and mortar to compress the curable resin composition of making, make flap.Particularly, exist
mortar in put into the title complex of specified amount, with 100kg/cm
2pressure compress 5 seconds from above with pestle, obtain thus the flap of prescribed volume.
(mensuration of flap characteristic)
(1) viscosity: judge by referring to touch qualitatively.
(2) the resistance to failure load of flap (strength at break) (g): in the mensuration of flap intensity, use the flap that is compressed into the shape of Φ 13mm, height 0.75cm with flap fabrication tool with the pressure of 0.39MPa.As determinator, use Systems Ltd. system, Texture Analyser, Model TA XT plus, as probe, use Cylinder probe P/2 (2mm Φ stainless steel).In the central authorities that are placed in the flap on level and smooth face, with trial speed, 1mm/s is pressed into probe, keeps 5 seconds in the time reaching certain force.Carrying out 3 times measures.Put on the load of flap take 100g as unit increase, in whole 3 times are measured, will on flap, not have the abnormal appearance such as crack, distortion and probe not to be set as the resistance to failure load of flap (g) to the ultimate load in flap when bottom.
(3) deep distance (mm): 3 mean values of the deep distance of the probe when being pressed into probe with the resistance to failure load of flap in flap are set as deep distance (mm).
[table 2]
(mensuration of helicoidal flow)
Curable resin composition of the present invention is compressed with the flap fabrication tool being made up of pestle and mortar of teflon system, make the flap of diameter 38mm.Then, this flap is dropped in the tank of Co., Ltd.'s god's made transmission forming mill of rattan metal industry (model: ETA-20, diameter of plunger: 40mm), measure the data of helicoidal flow.With regard to the shape of helicoidal flow mould, as cross-sectional shape, be set as the semi-circular shape of width 3mm × degree of depth 1.5mm.Be explained, molding condition setting is: 170 ℃ of die temperatures, transmission of pressure 7MPa, 120 seconds set times.
(manufacturing process of MAP product)
The effective lead frame of light-emitting diodes of the Cu system of longitudinal 50mm of plating Ag, horizontal 55mm, thickness 0.25mm has been carried out in preparation.Utilize transfer die to carry out under the following conditions curable resin composition and lead frame integrally formed.MAP after shaping (Mold Array Package: semi-conductive encapsulation has in fact the type in the shape of the one side shaping resin of metal) contains in longitudinal 15 row, horizontal 12 row and adds up to 180 reverberators.Each reverberator is upper surface
bottom surface
(angle of taper: 15 degree), height 0.55mm, be longitudinally provided with the electrode narrow slit that makes comprising of width 0.20mm curable resin composition of the present invention solidify the mixture forming apart from right-hand member 0.45mm place along trans D.Interval between each reverberator is 1.1mm in diametric(al) in length and breadth.With regard to lead frame and mould, as long as can make the reverberator with lead frame that meets above-mentioned prerequisite, be just not particularly limited.This molding shape is called to 3030MAP type.The concept map of molding is shown in to Fig. 1.
Transmitting shaping uses APIC YAMADA CORPORATION G-Line manual processed press and implements (clamp force 30ton, injection pressure 8MPa, injection speed 3mm/s).Metering white compound 5.0g, is cylindric by its figuration (the sheet materialization of above-mentioned record), is packed in barrel and forms.Molding condition setting is 170 ℃, 150 seconds.After shaping, in hot-air oven at 180 ℃ after fixing (after cure) 1 hour.
(warpage)
With regard to the warpage of MAP product, with forming section on while being placed on even surface, the state that will observe from positive side forming section is that recessed situation is defined as positive warpage, is defined as reflex action song for protruding situation.With regard to the degree of warpage, MAP product are placed on even surface, the value (mm) of the 4 limit middle distance maximums of leaving face is quantized.
(method of resistance to bend(ing) test)
Preparation external diameter is
the metal solid cylinder of width 55mm.Be pressed into lentamente the MAP product that obtain along this external diameter with two hands, observe whether occur crackle in ester moulding part.Situation about not cracking is judged to be to zero, situation about cracking is judged to be ×.
(mensuration of curved characteristic)
From using transfer molding machine and the dull and stereotyped thick flat board of 1mm of making of mould, by the aforesaid method that is shaped same with MAP to cut test film, so that the length of test film is below the above 80mm of 50mm, width is about 7mm to 8mm, relative 2 limits are parallel.As shown in Figure 2, between the metal fulcrum of fillet rectangular parallelepiped, so that the rectangular mode that is shaped as forming between fulcrum arranges test film.To test film width and thickness, measure 3 places that enter the test film between fulcrum to 0.01mm, mean value is separately set as to measurement result.Calculate area by test film width and thickness.With the Physical Property Analysis instrument processed TA.plus of Stable Micro Systems company, use the pressurization wedge being formed by the glass right-angle triangle processed of the fillet of width 10mm, speed applied load to the central authorities of test film with 2.0mm/sec, the load (fracture load by bending N) when determination test sheet fractures and destroy displacement (amount of bow mm when destruction).The value of 3 mensuration is averaged, be set as measurement result.Flexural failure intensity σ
b(N/mm
2) as described in following, calculate.
σ
b=M/I×h/2=(wl/4)/(bh
3/12)×h/2
At this, w is that fracture load by bending (N), l are that length of support is that member section lengthwise (mm), b are that member section is grown crosswise (mm), M is bending moment, I is 2 times, cross section moment from (mm), h.
(mensuration of hardness)
Hardness is measured based on JIS K7125, use D type shore hardness tester.Test film use overlapping 6 above 1mm thickness by the transmission test film that obtains of flat board of making that is shaped.
(measuring method of coefficient of linear expansion)
From using the flat board of transfer molding machine and the dull and stereotyped thickness 1mm making of mould, by the aforesaid method that is shaped same with MAP, with the square working sample that cuts of length of side 5mm × 5mm, use Rigaku Corporation Thermoplus-TMA8510 processed, measure at 0 ℃～250 ℃ with 10 ℃/min of compact models, 2gf load, heat-up rate.The mean value of α 1 coefficient of linear expansion during at 140 ℃～160 ℃ at 30 ℃～50 ℃, α 2 is set as to coefficient of linear expansion.
(mensuration of luminous reflectance factor)
For the each encapsulation obtaining by above-mentioned shaping, use small light splitting colour-difference meter (the Japanese electricity Se VSS400 processed of Industrial Co., Ltd) to measure the luminous reflectance factor in wavelength 400nm～700nm (interval 20nm).
At this, the measured value of each wavelength adopts any 4 places of encapsulation upper surface (to measure area
the mean value of measured value.In addition, the luminous reflectance factor after various long duration tests is obtained similarly.
By the table 2 that the results are shown in of the luminous reflectance factor of 480nm.
(long duration test)
As long duration test, utilize following method to carry out oven test and fast light test.Be explained, the luminous reflectance factor of the wavelength 480nm before long duration test is set as to initial stage reflectivity.
In addition, obtain the conservation rate of the luminous reflectance factor after long duration test.For example, utilize following calculating formula to obtain luminous reflectance factor after oven test (heating the test of 24 hours in the baking oven of the 180 ℃) conservation rate with respect to the luminous reflectance factor at initial stage.
Conservation rate (%)=(luminous reflectance factor after oven test)/(luminous reflectance factor at initial stage) × 100
(oven test)
By the sample of making as mentioned above (in air) slaking 24 hours in Temperature Setting is the convection oven of 180 ℃.,, measure the luminous reflectance factor of wavelength 480nm thereafter.
(fast light test: metal fluorescent tube)
Use SUGA Test Instruments Co., the weather-proof machine of Ltd. metal fluorescent tube processed (Metaling Weather Meter) (model M6T).To the sample of making described above with 120 ℃ of black panel temperature, radiation illumination 0.53kW/m
2expose to accumulation radiation illumination 50MJ/m
2, thereafter, measure the luminous reflectance factor of wavelength 480nm.
As shown in Table 2, all the warpage of the MAP product of embodiment is all little, therefore the cured article, being obtained by curable resin composition of the present invention can be realized linear expansion rate par or its following linear expansion rate with the Cu as base materials such as LED base plate for packaging.On the other hand, in comparative example 1, warpage is large, therefore, can confirm to use in the present invention the effect of (D) composition.It is, known that can to obtain warpage while having (D) composition be the semiconductor packages below 1.0mm adding.Known by embodiment and comparative example, by being used as titanium oxide, the zinc oxide of representational white pigment, luminous reflectance factor in the early stage and all good after long duration test, is thought of as good base resin system from thermotolerance photostabilization aspect.On the other hand, the resistance to pliability test of comparative example 1～3 is poorer than embodiment, therefore can confirm to use the effect that there is no the specific silicidation compound of conduct (A) composition using in comparative example.Known in embodiment 3～6, with broken silicon-dioxide or small particle size silicon-dioxide, can improve flap characteristic by also.Known in embodiment 9, even if be used as the carbon black of black pigment, also can obtain not having in fact the MAP molding of warpage.
(embodiment 10～12 and comparative example 4)
Take the coordinating example based on table 3 as basis, make the embodiment 10～12 shown in table 4 and the curable resin composition of comparative example 4, curved characteristic, flexural strength, the continuous molding test of comparison of aforementioned and make (A)～(C) and (Z) the mixture thermofixation of composition and the physical property of the cured article that obtains.
(continuous molding test)
Below, continuous molding test is described.Implement continuously to transmit to be shaped by the method same with above-mentioned (manufacturing process of MAP product) and be shaped for 40 times, the outward appearance of the MAP product that are shaped by range estimation comparative observation the 1st time and the MAP product that are shaped for the 40th time, the situation that the situation MAP product that are shaped for the 40th time compared with the MAP product of the 1st time to equal outward appearance is judged to be ◎, have that 9 situations of sentencing down cohesion destroyed areas more than 50 μ m are judged to be zero, the situation at existence 10～20 places is judged to be △, exceed 20 places is judged to be ×.
(make (A)～(C) and (Z) the mixture thermofixation of composition and making method and the evaluation of physical property of the cured article that obtains)
By (A)～(C) and (Z) mixture of composition pour in the groove of the casting use obtaining with the organo-silicone rubber dividing plate (thickness 1mm) of 2 sheet glass clamping U fonts, under the condition of 180 ℃, 2 hours, make its thermofixation, obtain thus cured article.Cured article is taken out from groove, cut rectangular test film, to become width 5mm, length 30mm, use the storage elastic modulus at Measurement of Dynamic Viscoelasticity device (IT Meter & Controls, Inc. DVA200 processed, stretch mode, mensuration frequency 10Hz) mensuration second-order transition temperature and 150 ℃.Be explained, second-order transition temperature is set as the peak temperature of loss tangent.
From embodiment 10～12 and comparative example 4 relatively, the flexural strength of molding or make (A)～(C) and (Z) when the storage elastic modulus at the Tg of the mixture thermofixation of composition and the cured article that obtains and 150 ℃ is too high, although continuous molding excellence, the bending resistance characteristic of MAP product reduces.
In addition, compare known to embodiment 10,11 and embodiment 12, even if the flexural strength of molding is same degree, make (A)～(C) and (Z) composition mixture thermofixation and the cured article that the obtains high side of storage elastic modulus at 150 ℃ can give better continuous molding.
[table 3]
[table 4]
Claims (35)
1. a curable resin composition, is characterized in that, contains following substances as essential composition:
(A) in 1 molecule, contain at least 2 and there is reactive carbon-to-carbon double bond and molecular weight lower than 1000 silicon compound with SiH base;
(B) compound that contains at least 2 SiH bases in 1 molecule;
(C) hydrosilylation catalysts;
(D) in 1 molecule, contain at least 1 and there is reactive carbon-to-carbon double bond with SiH base, and molecular weight is more than 1000 silicoorganic compound; And
(E) inorganic filling material.
2. curable resin composition claimed in claim 1, it also contains: (Z) in 1 molecule, contain at least 2 and have the organic compound of reactive carbon-to-carbon double bond with SiH base.
3. the curable resin composition described in claim 1 or 2, wherein, (D) composition is the straight chain shape polysiloxane endways with vinyl.
4. the curable resin composition described in any one in claim 1～3, wherein, (D) weight-average molecular weight of composition is more than 2,000 and 1,000, below 000.
5. the curable resin composition described in any one in claim 1～4, wherein, (E) composition is spherical silicon dioxide.
6. the curable resin composition described in any one in claim 1～5, it also contains: (F) white pigment.
7. curable resin composition claimed in claim 6, wherein, (F) median size of composition is below 1.0 μ m.
8. the curable resin composition described in claim 6 or 7, wherein, (F) composition is titanium oxide.
9. curable resin composition claimed in claim 8, wherein, (F) composition is for to have carried out surface-treated titanium oxide by organo-siloxane.
10. curable resin composition claimed in claim 8, wherein, (F) composition is for having carried out surface-treated titanium oxide with mineral compound.
11. curable resin compositions claimed in claim 10, wherein, (F) composition is for having carried out surface-treated titanium oxide with aluminum compound.
Curable resin composition described in 12. claims 6 or 7, wherein, (F) composition is at least one being selected from zinc oxide, zirconium white, strontium oxide, niobium oxides, boron nitride, barium titanate and barium sulfate.
Curable resin composition in 13. claims 1～12 described in any one, it also contains (G) metallic soap.
Curable resin composition described in 14. claims 13, wherein, (G) composition is Metallic stearates.
Curable resin composition described in 15. claims 14, wherein, (G) composition is to be selected from more than one in calcium stearate, Magnesium Stearate, Zinic stearas and aluminum stearate.
Curable resin composition in 16. claims 1～15 described in any one, wherein, with respect to (A) composition and (B) weight of the total of composition, (D) weight of composition is more than 30 % by weight.
Curable resin composition in 17. claims 1～16 described in any one, wherein, (E) more than the amount of the total of composition accounts for 70 % by weight of curable resin composition entirety.
Curable resin composition in 18. claims 6～17 described in any one, wherein, (F) content of composition be account for 10 % by weight of curable resin composition entirety more than.
Curable resin composition in 19. claims 13～18 described in any one, wherein, (G) content of composition is 0.01～5 % by weight that accounts for curable resin composition entirety.
Curable resin composition in 20. claims 1～19 described in any one, wherein, the surperficial reflection of light rate that is 480nm to wavelength of solidifying the molding forming is more than 80%.
Curable resin composition described in 21. claims 20, wherein, the conservation rate of the luminous reflectance factor after the oven test of 180 ℃, 24 hours (luminous reflectance factor × 100 at the luminous reflectance factor/initial stage after oven test) is more than 90%.
Curable resin composition in 22. claims 1～21 described in any one, is characterized in that, solidifies the flexural strength of the molding forming at 20N/mm
2～50N/mm
2scope in.
Curable resin composition in 23. claims 2～22 described in any one, it is characterized in that, the Tg of the mixture thermofixation of the composition of (A) composition～(C) and (Z) composition and the cured article that obtains is in the scope of 30 ℃～100 ℃.
Curable resin composition described in 24. claims 23, it is characterized in that, the mixture thermofixation of the composition of described (A) composition～(C) and (Z) composition and the cured article that obtains, the storage elastic modulus of measuring under the frequency 10Hz of 150 ℃, stretch mode is in the scope of 20MPa～100MPa.
Curable resin composition in 25. claims 1～24 described in any one, wherein, is shaped and while having made encapsulation at the one side of the effective lead frame of light-emitting diodes, and the warpage of encapsulation is ± below 1.0mm.
Curable resin composition in 26. claims 1～25 described in any one, it is for semi-conductive encapsulation.
27. 1 kinds of flaps, it comprises the curable resin composition described in any one in claim 6～26, and described flap is characterised in that:
(A) composition and (B) composition in the two one of be at least 23 ℃ time viscosity be the liquid below 50Pa second,
(E) composition and (F) content of the total of composition be 70～95 % by weight,
Particle below 12 μ m account for (E) composition and (F) ratio of the total of composition be more than 40 volume %.
28. 1 kinds of moldinies, is characterized in that, it forms for the curable resin composition described in any one in claim 1～25 solidifies, and the reflection of light rate to wavelength 480nm on surface is more than 90%.
29. 1 kinds of semi-conductive encapsulation, is characterized in that, right to use requires the curable resin composition described in 26 be shaped and obtain.
30. 1 kinds of semi-conductive encapsulation, is characterized in that, right to use require curable resin composition described in 26 and metal integrally formed and obtain.
The encapsulation of the semiconductor bulk described in 31. claims 29 or 30, wherein, utilizes transfer mould integrally formed and obtain curable resin composition and lead frame.
Semi-conductive encapsulation in 32. claims 29～31 described in any one, its encapsulation for forming at the one side shaping resin of metal in fact.
33. 1 kinds of semi-conductive encapsulation, it is that right to use requires curable resin composition described in 26 to carry out transfer mould to form.
34. 1 kinds of semiconductor devices, its right to use requires the semi-conductive encapsulation described in any one in 29～33 to manufacture.
35. 1 kinds of photodiodes, its right to use requires the semi-conductive encapsulation described in any one in 29～33 to manufacture.
Applications Claiming Priority (5)
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| JP2011-220035 | 2011-10-04 | ||
| JP2011220035 | 2011-10-04 | ||
| JP2012-141409 | 2012-06-22 | ||
| JP2012141409 | 2012-06-22 | ||
| PCT/JP2012/075633 WO2013051600A1 (en) | 2011-10-04 | 2012-10-03 | Curable resin composition, tablet of curable resin composition, molded body, semiconductor package, semiconductor component and light emitting diode |
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| Publication Number | Publication Date |
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| CN103842442A true CN103842442A (en) | 2014-06-04 |
| CN103842442B CN103842442B (en) | 2018-08-24 |
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| JP (1) | JP6043292B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109585685A (en) * | 2018-12-07 | 2019-04-05 | 纳晶科技股份有限公司 | Light takes out structure, its production method and luminescent device |
| CN109844029A (en) * | 2016-08-08 | 2019-06-04 | 道康宁东丽株式会社 | Curability granulated silicone composition, the light reflecting material being made of it and its manufacturing method |
| CN113574115A (en) * | 2019-12-18 | 2021-10-29 | 富士高分子工业株式会社 | Thermally conductive composition and method for producing same |
| TWI757112B (en) * | 2021-03-08 | 2022-03-01 | 日商富士高分子工業股份有限公司 | Thermally conductive composition and method for producing the same |
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| JP5735423B2 (en) * | 2009-07-15 | 2015-06-17 | 株式会社カネカ | Curable composition for optical materials |
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| WO2011125753A1 (en) * | 2010-04-02 | 2011-10-13 | 株式会社カネカ | Curable resin composition, curable resin composition tablet, molded body, semiconductor package, semiconductor component and light emitting diode |
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| CN101389695A (en) * | 2006-02-24 | 2009-03-18 | 陶氏康宁公司 | Light emitting device encapsulated with silicones and curable silicone compositions for preparing the silicones |
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| CN109844029A (en) * | 2016-08-08 | 2019-06-04 | 道康宁东丽株式会社 | Curability granulated silicone composition, the light reflecting material being made of it and its manufacturing method |
| CN109585685A (en) * | 2018-12-07 | 2019-04-05 | 纳晶科技股份有限公司 | Light takes out structure, its production method and luminescent device |
| CN109585685B (en) * | 2018-12-07 | 2021-06-01 | 纳晶科技股份有限公司 | Light extraction structure, manufacturing method thereof and light emitting device |
| CN113574115A (en) * | 2019-12-18 | 2021-10-29 | 富士高分子工业株式会社 | Thermally conductive composition and method for producing same |
| CN113574115B (en) * | 2019-12-18 | 2022-10-28 | 富士高分子工业株式会社 | Thermally conductive composition and method for producing same |
| TWI757112B (en) * | 2021-03-08 | 2022-03-01 | 日商富士高分子工業股份有限公司 | Thermally conductive composition and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2013051600A1 (en) | 2015-03-30 |
| JP6043292B2 (en) | 2016-12-14 |
| CN103842442B (en) | 2018-08-24 |
| TW201323526A (en) | 2013-06-16 |
| TWI625363B (en) | 2018-06-01 |
| WO2013051600A1 (en) | 2013-04-11 |
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