CN1962798B - Epoxy resin adhesive composition and optical semiconductor adhesive adopting same - Google Patents
Epoxy resin adhesive composition and optical semiconductor adhesive adopting same Download PDFInfo
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- CN1962798B CN1962798B CN 200610150389 CN200610150389A CN1962798B CN 1962798 B CN1962798 B CN 1962798B CN 200610150389 CN200610150389 CN 200610150389 CN 200610150389 A CN200610150389 A CN 200610150389A CN 1962798 B CN1962798 B CN 1962798B
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Abstract
The present invention relates to an epoxy resin bonded compound and an optical semiconductor binding agent thereof. The combination can restrain the short wavelength absorptivity, has excellent ultraviolet resistance, weathering resistance, light permeability and storage stability, which is used in the semiconductor device full of optical semiconductor chip and bonding of a variety of parts and has excellent coating character and transmission capacity for the wavelength emergent from the optical semiconductor. Provided is a epoxy resin bonded compound which has an alicyclic ring type epoxide (A), a silicane compound (B) for the hydrolysis group connected to the silicon atom, a 2-valent organo-tin compound (c1), a 4-valent organo-tin compound (c2) and the an inorganic filler (D) with light permeability as the required component, characterized in that, based on the gross of the combination, the content of each component is: (A) is 30-95%, (B) is 0.1-15%, (c1) 0.01-5%, (c2) 0.01-5% and (D) 0.1-50%.
Description
Technical field
The present invention relates to the epoxy bond compsn and adopt its optical semiconductor to use sticker; More particularly; Relate to and a kind ofly can suppress short wavelength's absorptivity; Ultraviolet resistance, weathering resistance, thermotolerance, light transmission and fine properties can be used in the assembling of the semiconductor device that optical semiconductor chip is housed and the bonding of various parts, have good screening characteristics; To the good epoxy bond compsn of transmissivity of the wavelength that sends by optical semiconductor, and adopt its optical semiconductor to use sticker.
Background technology
The optical semiconductor that with photodiode (LED) and laser diode etc. is representative is processed by compounds such as GaP system, GaAlAs system, GaInAlAs system, GaInAlP systems, and it structurally must can be from semi-conductor end face and bottom surface galvanization.
When being bonded in these LED etc. on lead frame or the substrate; The composition epoxy resin that is referred to as conductive adhesive is used as the energising sticker and uses; Bondings such as bottom surface through making LED etc. and lead frame, substrate can be carried out luminous reflectance, conducting electric current and heat.And,, use the fine lead of the materials such as metal that are referred to as filament to connect LED and lead frame and substrate, thereby can conduct at the end face of LED etc.
These existing LED can send infrared wavelength to green intensity, are considered to very difficult but will send the wavelength shorter than green morely.
But, along with technical renovation in recent years, find that GaN based semiconductor compound is more to send the wavelength shorter than green.These GaN based semiconductor compounds can send the wavelength below about 550nm fully, can send green, blue or ultraviolet equiwavelength.
GaN based semiconductor compound is that structures such as LED are different with above-mentioned GaP; Because situation about can switch on from the bottom surface and situation about needn't switch on are arranged; Thereby with lead frame, substrate bonding the time, it uses above-mentioned conductive adhesive, the composition epoxy resin that do not possess electroconductibility bonds.
But conductive adhesive in the past, composition epoxy resin be because the main general epoxy resin such as bisphenol A type epoxy resin, phenol aldehyde type epoxy resin that use, thereby if life-time service then can produce the problem of variable color.The reason of variable color is considered to because general epoxy resin has absorbed the wavelength below 500～450nm, and the energy of this absorption makes the structure of epoxy resin that the cause that changes take place.And owing to absorbed wavelength energy, make the light that sends from LED etc. decay the problem that generation can not be shinny to some extent.
And; Because the wavelength that GaN based semiconductor compound sends will send to the outside mostly; Thereby necessarily require conductive adhesive, composition epoxy resin reflection wavelength more, perhaps make the composition epoxy resin transmission peak wavelength, thereby the agglutinating substrate portion is reflected more.
On the other hand,, also have and use alicyclic epoxy resin, hydrogenation type epoxy resin, use acid anhydride type curing agents such as methylhexahydrophthalic anhydride or norbornene dicarboxylic anhydride usually in order to address these problems.
At this moment, can obtain transparent cured article, thereby can obtain the good cured article of transmissivity, but when be mixed into single component, then exist the applicable time to shorten and the problem of operation aspect.In addition, through use dicyano diamide, phenol solidifying agent etc., make that being mixed into single component also becomes possibility, still, it is painted cured article to occur, thereby absorbs the wavelength below 500～450nm, makes the problem of sending reflection of light rate decline aspect.
In addition, the LED that sends red extremely blue all looks is by practicability, and it has been conceived to be widely used for the open air as teleseme, informatiom board etc.Therefore, press for the weathering resistance that improves composition epoxy resin.
For this reason, the composition epoxy resin (for example, referring to patent documentation 1) be made up of hydrogenation type epoxy resin, cationic polymerization initiators, aromatic series salt, phenol inhibitor, phosphorus compound has been proposed.If use said composition, then think and to avoid to obtain the cured article of weathering resistance, good-toughness owing to coloring resin with owing to receive thermal process and painted problem.
But, contain in the cationic polymerization initiators sulphur compound, phosphorus compound, halogenide, ammonium ion these as the preferred element of electronic material.The solvability of aromatic series salt in resin is not high enough, and be reactive inhomogeneous; It is medium that metals ion remains in resin cured matter, can become problem.In addition, though the phenol inhibitor has the effect that improves weathering resistance, exist in time and the discoloration problem of flavescence.In addition, phosphorus compound is the meeting ionize under certain condition, when forming semi-conductor and compound, may produce trouble.
In order to address these problems, to have proposed to comprise and contained containing epoxy compounds, contain silanol groups and/or directly being connected the compound of the hydrolization group on the Siliciumatom and the composition epoxy resin of organic tin compound of ester ring type epoxy group(ing).(referring to patent documentation 2)
Therefore the cured article of this composition epoxy resin is suitable as coating usefulness because the transparency is also good, thinks that it is good to make it become weathering resistance, and the also good compsn of package stability through using the alicyclic epoxy compound.But the cured article about 120～150 ℃ does not possess bonding force, and in order to obtain bonding force, must be heated to more than 200 ℃, therefore, points out can not be used to adopt the electronic unit of organic substrate.
In addition; Proposed a kind ofly to form and contain with the conductive paste of silver type powder as this electroconductive powder by organic tackiness agent, solvent and/or monomer and electroconductive powder; In this conductive paste; With respect to resin solid content, contain 0.1～10% intramolecularly and have 1 above benzotriazole skeleton and have methacryloxy or the compound of hydroxy functional group (for example, referring to patent documentation 3).
And; As relative insulativity paste; Propose ultraviolet resistance, insulativity paste (referring to patent documentation 4) that weathering resistance is good, contained the effect of the compound composition performance UV light absorber of benzotriazole skeleton, be used to improve ultraviolet resistance, weathering resistance.But, in order to improve the reflectivity of optical semiconductor wavelength light, must further improve ultraviolet resistance, weathering resistance, make it not absorb ultraviolet ray.
For this reason, having developed before the present inventor with alicyclic epoxy resin, acylhydrazine class solidifying agent and light reflective mineral filler is the composition epoxy resin (referring to patent documentation 5) of essential composition.Like this, can obtain can rejection ratio short wavelength's absorptivity more in the past, light reflective, ultraviolet resistance, the sticker that weathering resistance is good.
On the other hand, former optical function device adopts the epoxy resin that does not contain mineral filler to seal mostly in order to ensure the transparency of resin layer.In this case; If consider the thermotolerance wet fastness low-stress property of cured article etc.; It is enough good then must not to say so; So developed the transparent joint filling material that contains mineral filler, proposed in epoxy resin, curing catalyst, the epoxy resin of mineral filler, to adopt the specific refractory power of compsn cured article and the composition epoxy resin (referring to patent documentation 6) that temperature varying coefficient satisfies the particular kind of relationship formula thereof as essential composition.Like this, its cured article all keeps the higher transparency under all temps environment, and thermotolerance, wet fastness, low-stress property are good.
But, for the situation of epoxy adhesive used in the optical function device, particularly optical semiconductor; If surpassing long-time placement the under 100 ℃ the high temperature, then resinous principle meeting variable color, and; Also make the resinous principle variable color owing to absorb the short wavelength; Thereby the situation that light transmission descends occurs, therefore press for to develop and have better thermotolerance, can prevent the composition epoxy resin that light transmission descends.
[patent documentation 1] spy opens 2001-342240 (claim of patent)
[patent documentation 2] spy opens flat 8-3452 (claim of patent)
[patent documentation 3] spy opens 2001-332124 (claim of patent)
[patent documentation 4] spy opens 2001-316596 (claim of patent)
[patent documentation 5] spy opens 2004-256603 (claim of patent)
[patent documentation 6] spy opens 2002-88223 (claim of patent)
Summary of the invention
The objective of the invention is in view of above-mentioned prior art problems; Provide a kind of and can suppress short wavelength's absorptivity; Cohesiveness, ultraviolet resistance, weathering resistance, thermotolerance and fine properties can be used in the assembling of the semiconductor device that optical semiconductor chip is housed and the bonding of various parts, have good screening characteristics; To the good epoxy bond compsn of transmissivity of the wavelength that sends by optical semiconductor, and adopt its optical semiconductor to use sticker.
The present inventor has carried out deep research repeatedly in order to reach above-mentioned purpose; The result finds; If organo-tin compound and the specific light transmission mineral filler of organo-tin compound, 4 valencys that will have the silane compound that directly is connected the hydrolization group on the Siliciumatom, divalent is mixed in the alicyclic epoxy compound with specific amount as essential composition, though then the gained composition epoxy resin place under 100～120 ℃ the high temperature also not can variable color; And find; If it use sticker as optical semiconductor, then owing to can suppressing short wavelength's absorptivity, and light transmission, ultraviolet resistance, weathering resistance, thermotolerance and package stability, cohesiveness are good; Thereby can being preferably applied to nearest technological development, to make progress significant GaN be among the LED, thereby accomplished the present invention.
Promptly; According to the 1st invention of the present invention, a kind of epoxy bond compsn is provided, it is the mineral filler (D) that a kind ofly contains alicyclic epoxy compound (A), have the silane compound (B), organo-tin compound (C) and the light transmission that directly are connected the hydrolization group on the Siliciumatom as the epoxy bond compsn that is used for optical semiconductor that must composition; Wherein organo-tin compound (C) is the mixture of organo-tin compound (c2) of organo-tin compound (c1) and 4 valencys of divalent; And based on total composition, the content of above-mentioned each composition is that (A) is 30～95 weight %; (B) be 0.1～15 weight %; (c1) being 0.01～5 weight %, (c2) is 0.01～5 weight %, and (D) is 0.1～50 weight %.
And, according to the 2nd invention of the present invention, a kind of epoxy bond compsn is provided, it is characterized in that silane compound (B) is the silane compound of nonnitrogenous atom in the 1st invention.
And, according to the 3rd invention of the present invention, a kind of epoxy bond compsn is provided, it is characterized in that in the 1st or the 2nd invention silane compound (B) is for containing the alkoxysilane compound containing trialkylsilyl group in molecular structure that 2 or 3 carbonatomss are 1～3 hydrolization group.
And,, a kind of epoxy bond compsn is provided according to the 4th invention of the present invention; It is characterized in that in the 1st invention; The combined amount of the organo-tin compound (c2) of organo-tin compound of divalent (c1) and 4 valencys is in wt ratio, (c2)/(c1)=1～20.
And, according to the 5th invention of the present invention, a kind of epoxy bond compsn is provided, it is characterized in that in the 1st invention, the primary particle median size of mineral filler (D) is below the 3.0 μ m.
In addition,, a kind of epoxy bond compsn is provided, it is characterized in that the band-gap energy of mineral filler (D) is more than the 2.8eV in the 1st or the 5th invention, and specific refractory power is 1.2～1.8 according to the 6th invention of the present invention.
On the other hand, according to the 7th invention of the present invention, provide the optical semiconductor that adopts the 1st～6 any one epoxy bond compsn to make to use sticker.
The epoxy bond compsn of the application of the invention can obtain cohesiveness, to the absorbefacient inhibition of short wavelength, ultraviolet resistance, weathering resistance, light transmission, excellent heat resistance, and the good cured article of screening characteristics.And, use its optical semiconductor to use sticker, can improve the optical characteristics and the safety of the GaN based semiconductor that sends the following short wavelength of 550nm especially significantly, therefore commercial value of the present invention is very big.
Embodiment
Below, carry out bright specifically with sticker to epoxy bond compsn of the present invention and the optical semiconductor that adopts it.
1. epoxy bond compsn
Epoxy bond compsn of the present invention is the epoxy bond compsn that contains alicyclic epoxy compound (A), has the silane compound (B) that directly is connected the hydrolization group on the Siliciumatom, uses in the optical semiconductor of the organo-tin compound (c2) of the organo-tin compound (c1) of divalent, 4 valencys and light transmission mineral filler (D) with specific ratios separately.And, in addition adjust viscosity if desired, then can also add compositions (E) such as epoxy compounds beyond the ester ring type, solvent, thinner, viscosity modifier.
(A) alicyclic epoxy compound
The alicyclic epoxy compound is the thermosetting resin with alicyclic moieties such as hexanaphthene and epoxy moieties.Below, the alicyclic epoxy compound is also referred to as alicyclic epoxy resin.
As this alicyclic epoxy compound, can use two keys with cyclohexene ring to carry out the oxidation epoxidation and aliphatics cyclic rings epoxy resins of obtaining etc. with Peracetic Acid.For example, can enumerate 3,4-epoxycyclohexyl-3 ', gathers (epoxidized cyclohexene oxide compound) etc. at 4 '-cyclohexane carboxylate.Also can use the alicyclic epoxy resin that does not have record here.These alicyclic epoxy compounds can use separately, and it is also no problem to mix use.
In addition, in above-mentioned patent documentation 6, the epoxy resin that contains 1 above naphthalene nucleus in preferred use 1 molecule is disclosed.Under the situation of using this naphthalene-ring containing epoxy compounds, if excessive interpolation then can cause naphthalene nucleus to absorb the luminous short wavelength who produces of LED, because of the resin variable color makes degradation under the reflectivity.
In the present invention, the content of alicyclic epoxy compound must be 30～95 weight %.The content of alicyclic epoxy compound is when less than 30 weight %, and then other composition increases relatively, if the silane compound of coupling increases; The situation of cohesive strength decline then can occur causing,, then cause keeping quality to descend if the organo-tin compound of coupling increases; Moreover; If the mineral filler of coupling increases, then viscosity increases, the screening characteristics variation.In addition, if surpass 95 weight %, then other composition reduces relatively, thereby has the possibility that can not carry out sufficient curing reaction.The preferred content of alicyclic epoxy resin is the scope of 40～90 weight %.
(B) silane compound
The silane compound that uses among the present invention is meant and contains the compound that can produce the group of silanol groups through hydrolysis.And so-called here silanol groups is meant the hydroxyl that directly is connected on the Siliciumatom.
As the example of this silane compound, usually, can enumerate the vinyltrimethoxy silane, the vinyltriethoxysilane that contain vinyl; The 3-glycidoxypropyltrime,hoxysilane, the 3-glycidoxy propyl-triethoxysilicane that contain epoxy group(ing); The 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyldiethoxysilane, the 3-methacryloxypropyl triethoxyl silane that contain methacryloxy; Or as tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, dimethyldimethoxysil,ne, dimethyldiethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, hexyl Trimethoxy silane, hexyl triethoxyl silane, decyl Trimethoxy silane, the decyl triethoxyl silane of alkoxysilane compound containing trialkylsilyl group in molecular structure; Or, do not have the material of record here as the METHYL TRICHLORO SILANE of halogenated silanes, dimethyldichlorosilane(DMCS), trimethylchlorosilane, phenyl-trichloro-silicane, diphenyl dichlorosilane etc., if can produce silanol groups, then also can use through hydrolysis.
Wherein, especially preferably contain the alkoxysilane compound containing trialkylsilyl group in molecular structure that 2 or 3 carbonatomss are 1～3 hydrolization group.Containing carbonatoms is the alkoxysilane compound containing trialkylsilyl group in molecular structure of the hydrolization group more than 4 or their low polycondensate, because it is therefore preferred to expect to improve cohesive strength.In addition, these contain the silane compound that directly is connected the hydrolization group on the Siliciumatom mix more than 2 kinds use also no problem.
Silane compound contains the hydrolization group that directly is connected on the Siliciumatom in the present invention, and it plays a role as making the part of alicyclic epoxy resin solidified catalyzer, and therefore making the content of silane compound is 0.1～15 weight %.If this compositing range, then according to the amount of epoxy resin, it can play a role as curing catalysts effectively.If less than 0.1 weight % then can not bring into play the effect of catalyzer, thereby alicyclic epoxy resin can not solidify.On the other hand, if surpass 15 weight %, then excessive silane compound is present in the cured article, causes cohesive force to descend.
In addition, in the present invention,, can suppress better the silane compound that uses nonnitrogenous atom by UV-induced discolouration and the discolouration that causes by heat if as above-mentioned silane compound, then can knowing.Though not necessarily clear and definite, its reason also can be expected causing painted owing to the molecular linkage that ultraviolet ray, hot energy destroy around the nitrogen element.
(C) organo-tin compound
In the present invention, organo-tin compound is made up of the organo-tin compound (c1) of divalent and the organo-tin compound (c2) of 4 valencys, and with specific ratio mixed.
(c1) organo-tin compound of divalent
Commercially available organic cpds as the organo-tin compound of divalent, it had no particular limits in the present invention, so long as can use.As concrete example, can enumerate oxalic acid tin, two butyric acid tin, two stannous octoates, two LAURIC ACID 99 MIN tin, distearyl acid tin, naphthenic acid tin etc.It is also no problem that they mix more than 2 kinds.
The organo-tin compound of divalent and above-mentioned silane compound likewise play a role as a part that makes alicyclic epoxy resin solidified catalyzer.Therefore making the content of the organo-tin compound of divalent is 0.01%～5 weight %.If this scope, then any divalent organo-tin compound all can be brought into play the effect of catalyzer.On the other hand, if less than 0.01 weight % then can not bring into play the effect of catalyzer because content is very few,,, thereby produce storage property problem then owing to content too much makes reactive the raising if surpass 5 weight %.
(c2) organo-tin compound of 4 valencys
As the 4 valency organo-tin compounds that use among the present invention, so long as commercially available organic cpds can use.As concrete example, can enumerate tetraacethyl tin, four stannous octoates, April cinnamic acid tin, nitrilotriacetic butyl pink salt, three butyric acid butyl pink salts, three sad butyl pink salts, three LAURIC ACID 99 MIN butyl tin salt, nitrilotriacetic octyl group pink salt, three butyric acid octyl group pink salts, three sad octyl group pink salts, three LAURIC ACID 99 MIN tin octylate salt, dibutyltin diacetate salt, two butyric acid dibutyl pink salts, two sad dibutyl pink salts, dibutyl tin laurate salt, oxalic acid dioctyl pink salt, two butyric acid dioctyl pink salts, two sad dioctyl pink salts, two LAURIC ACID 99 MIN dioctyl tin salt, toxilic acid dibutyl pink salt, three butyric acid phenyl pink salts, three LAURIC ACID 99 MIN phenyltin salt, butyl tin front three oxide compound, butyl tin three fourth oxide compounds, tin octylate front three oxide compound, phenyltin front three oxide compound, dibutyl tin diformazan oxide compound, dioctyl tin diformazan oxide compound, dioctyl tin two tertiary carbon hydrochlorates, dibutyl tin two (trimethoxy silicate), dibutyl tin two (acetyl pyruvate), dibutyl tin two (neighbour-phenylphenol salt), dibutyl tin oxide, dioctyltin oxide etc.It is also no problem that they mix more than 2 kinds.
Owing to the organo-tin compound of 4 valencys also as the part of alicyclic epoxy resin solidified catalyzer is played a role, therefore making the content of the organo-tin compound of 4 valencys is 0.01%～5 weight %.If this scope, then any 4 valency organo-tin compounds can use as catalyzer.On the other hand, if less than 0.01 weight % then can not bring into play the effect of catalyzer because content is very few,,, thereby produce storage property problem then owing to content too much makes reactive the raising if surpass 5 weight %.
In the present invention, the organo-tin compound of the organo-tin compound of divalent and 4 valencys mixes use as essential composition with it.If the organo-tin compound of divalent, the organo-tin compound of 4 valencys are used separately, though then can obtain the cohesiveness cured article, when for the organo-tin compound of divalent; Package stability variation at room temperature, viscosity increases in use, on the other hand; When being the organo-tin compound of 4 valencys, same with the organo-tin compound of divalent, the situation of package stability variation under the room temperature can appear; Even perhaps fine properties; But in order to obtain enough cohesiveness, solidification value is necessary for the high temperature more than 200 ℃, thereby causes being used for the problem of the electronic unit that is made up of organic materials substrate etc.
By contrast; According to the present invention; Owing to the organo-tin compound of divalent and the organo-tin compound of 4 valencys are modulated this epoxy bond compsn with the specific ratios combination; Thereby this problem can not appear, and its fine properties, curing can obtain to have the cured article of high strength bond property under 120～150 ℃ low temperature.
For the organo-tin compound (c1) of divalent and the ratio of the organo-tin compound (c2) of 4 valencys, have no particular limits in the present invention, hope that the wt ratio of (c2)/(c1) is 1～20, particularly 1～10 scope.This is because if the organo-tin compound of divalent (c1) too much makes the wt ratio less than 1 of (c2)/(c1), then can occur as the package stability of the divalent organo-tin compound shortcoming situation of variation slowly.On the other hand, if the organo-tin compound of 4 valencys (c2) too much makes this wt ratio surpass 20, reactive situation about slowly descending can appear then.
These phenomenons are inferred to be: though the organo-tin compound of 4 valencys is compared with the organo-tin compound of divalent; Reactive relatively poor to epoxy resin; If but mix with the organo-tin compound of divalent with specific ratio, then when bonding, passing through heating, it will change to the divalent organotin of quite reactive.In addition,, thereby have the storage property of appropriateness, thereby it is specific to have a sufficient preservation because 4 valency organo-tin compounds have this reactivity.
(D) mineral filler
The mineral filler of using among the present invention is characterised in that it is the light transmission inorganic particulate.The intensity that this mineral filler owing to have can be used for improving epoxy resin cured product with regulate viscosity, and, therefore can bring into play the effect of thixotroping regulator to the non-absorbent basically characteristic of light, wavelength that LED etc. sends.
In the present invention, as mineral filler, more hope to use band-gap energy as more than the 2.8eV, specific refractory power is 1.2～1.8 inorganic particulate.The band-gap energy of inorganic particulate is more than the 2.8eV if this is, then inorganic particulate can not absorb the light of emission wavelength.Usually, mineral compound is to the absorption of wavelength, mainly results from the absorption that excites of semiconductor compound, and what be equivalent to this energy is the band-gap energy of mineral compound.If the not enough 2.8eV of this band-gap energy, the wavelength absorption territory that then this particle had is more than the 440nm, thereby in luminous LED etc., causes the absorption of light.
Usually the specific refractory power majority of epoxy resin is presented at about 1.5～1.6.Therefore, if use and the approaching specific refractory power of its specific refractory power are 1.2～1.8 inorganic particulate, then can obtain light transmission.The preferred especially and epoxy resin specific refractory power is equal about 1.5～1.6 inorganic particulate.If specific refractory power drops on beyond 1.2～1.8 scopes, the situation of light transmission then can appear obtaining.
Like this, if the inorganic particulate specific refractory power drops in the above-mentioned scope, the size of then tackling particle diameter does not have special restriction.If the specific refractory power of inorganic particulate drops on this beyond scope, the median size of then hoping primary particle is below the 3.0 μ m.If median size surpasses 3.0 μ m, then according to the kind of mineral filler, the situation that light transmission descends can appear.Therefore, the median size of mineral filler primary particle is below the 3.0 μ m, is preferably especially below the 0.8 μ m.If satisfy this condition, owing to can not stop light with 0.4～0.8 mum wavelength, thereby light transmission is not had influence basically.If the median size of primary particle is below the 0.4 μ m, and then be below the 0.25 μ m, then can further improve optical transmission property.
The primary particle of mineral filler exists preferablely separately dispersedly in the compsn, when it condenses when forming offspring, preferably takes measures such as mixed dispersant.In the present invention, situation about playing a role as dispersion agent with silane compound is also arranged.
In addition, the color of inorganic particulate is had no particular limits, but in order to prevent absorption optical wavelength, preferably the white color system powder or with its agglutinating LED etc. and the homochromy powder of emission wavelength.
As this inorganic particulate, can enumerate silicon fluoride, Natural manganese dioxide, aluminum oxide, silicon-dioxide etc.Wherein, particularly preferably be silicon-dioxide.These particles (powder) can use separately, but it is also no problem to mix use more than 2 kinds.
The addition of inorganic particulate is 0.1～50 weight %.This is because when addition arrived less than 0.1 weight % less, then mineral filler can not be brought into play the function of the thixotroping regulator of giving this compsn; On the other hand; If more than 50 weight %, then because thixotropy becomes too high, and viscosity also becomes too high; Thereby apply very difficulty, make the decline of operation property.Preferred content is 3～40 weight %, the more preferably scope of 5～30 weight %.
In above-mentioned patent documentation 2, though mixed organo-tin compound, it especially preferably only uses the compound of 4 valencys, and this is a kind of, and does not have the object lesson of illustration mineral filler.Therefore, as the low-temperature curing performance under 120～150 ℃ required in this invention, it is imperfect, thereby can not expect that it has the characteristic as sticker.
(E) other
In the present invention, as required, in the scope of influencing characteristic not, also can add epoxy compounds beyond the ester ring type of regulating viscosity, other resinous principle, solvent, thinner, viscosity modifier, dispersion agent etc.
These additives are divided into when curing reaction epoxy resin and additive or additive reaction itself and get in the cured article and do not get in the cured article two kinds, for getting in the cured article, preferably do not have phenyl ring in its structure.When having phenyl ring, if too much add, then phenyl ring absorbs the luminous wavelength that produces of LED, causes degradation under the reflectivity, therefore must be noted that its content.
As the additive that can get in the cured article, can enumerate phenyl glycidyl ether, 2-ethylhexyl glycidyl ether that single end in the structure contains epoxy group(ing); The neopentylglycol diglycidyl ether, 1 that perhaps contains 2 above epoxy group(ing) in the structure, the 6-hexanediol diglycidyl ether; Known epoxy resin such as the epoxy resin bisphenol A type epoxy resin beyond the ester ring type, bisphenol f type epoxy resin, phenol aldehyde type epoxy resin, hydrogenation type bisphenol A type epoxy resin etc.
On the other hand, for situation about not getting in the cured article, if when solidifying whole evaporable additives, it is all no problem then to have an any structure.
As not with the solvent of epoxy resin reaction; Can enumerate 2; 2,4-trimethylammonium-3-hydroxyl two pentane isobutyrates, 2,2; 4-trimethylpentane-1,3-isobutyrate, butyric acid isobutyl, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether or 2 hydroxy propanoic acid ethyl ester etc.
2. optical semiconductor is used sticker
Above-mentioned composition epoxy resin is applicable to the assembling of the semiconductor device that optical semiconductor chip is housed or the bonding of various parts.
Optical semiconductor of the present invention is used sticker; For for example optical semiconductors such as light receiving element, luminous element such as LED, phototransistor, photorectifier, opticcoupler, CCD (charge coupled cell), EPROM (Erasable Programmable Read Only Memory EPROM), optical pickocff, have the not available excellent adhesion of composition epoxy resin, hot strength, transmittance, discolouration in the past.Particularly if during the LED of the GaN system that is used to bond, can expect has fabulous effect.
The evaluation method of these characteristics (condition) will describe in following embodiment, and when cohesiveness is more than the 60N, hot strength is more than the 5N, and transmittance is more than 80%, it is good to be during discolouration (Δ E) less than 5.
Method of use to this sticker has no particular limits; Can be according to the difference of forming and difference; Can this epoxy bond compsn be dropped on the substrate, behind the loading optical semiconductor chip, for example; In 50～250 ℃ baking oven, placed 20～300 minutes, and perhaps on 150～300 ℃ hot-plate, placed its curing is got final product.
When in baking oven, being cured, if 50 ℃ of less thaies or less than 20 minutes, then adhesive cures is insufficient, if surpassing 300 minutes more than 250 ℃, the possibility that resinous principle decomposes then can occur.In addition, likewise when on hot-plate, being cured,, make curing insufficient, if, the possibility that resinous principle decomposes then can occur surpassing for 300 seconds more than 300 ℃ if can not carry out fully with next curing reaction at 150 ℃.
[embodiment]
Below, adopt embodiment, comparative example that the present invention is carried out concrete announcement, but thus the present invention is not carried out any qualification.In addition, used starting material are following:
Epoxy compounds
Alicyclic epoxy resin (a): 3,4-epoxycyclohexyl-3 ', 4 '-naphthenic acid ester.
Epoxy resin (b): bisphenol A type epoxy resin.
Silane compound
Silane compound (a): 3-glycidoxypropyltrime,hoxysilane.
Silane compound (b): 3-methacryloxypropyl trimethoxy silane.
Silane compound (c): 3-TSL 8330.
Organometallic compound
The organo-tin compound of divalent: two stannous octoates
The organo-tin compound of 4 valencys: nitrilotriacetic butyl pink salt
Organo-aluminium compound: three (ethyl acetoacetic acid) aluminium
Organic zirconate: methyl ethyl diketone zirconium
Mineral filler
Inorganic particulate (a): commercially available SiO 2 powder
Band-gap energy is more than the 2.8eV, and median size is the white powder of 0.2 μ m.
Inorganic particulate (b): commercially available cupric oxide powder
The not enough 2.8eV of band-gap energy, median size is the reddish-brown powder of 0.3 μ m.
Inorganic particulate (c): commercially available SiO 2 powder
Band-gap energy is more than the 2.8eV, and median size is the white powder of 3.1 μ m.
Other mixture
Anhydride curing agent: New Japan Chem Co., Ltd produces, MH-700.
Curing catalysts: quaternary phosphine bromide
Additive (a): the viscosity modifier of composition epoxy resin
Do not get into during curing reaction in the structure and the evaporable diethylene glycol monobutyl ether
Additive (b): the viscosity modifier of composition epoxy resin
Get into the bisphenol f type epoxy resin in the structure during curing reaction.
In addition, assessment item, evaluation method are following:
Cohesive strength:
The epoxy bond compsn is dropped on the stainless steel substrate, load the square silicon chip of 1.5mm, in 120 ℃ baking oven, placed 60 minutes, then, placement was cured in 60 minutes in 150 ℃ baking oven.After being cooled to room temperature, give the above-mentioned silicon chip application of force to above-mentioned stainless steel substrate from horizontal direction, the masterpiece when measuring this silicon chip and peeling off is a cohesive strength.If cohesive strength is then for qualified more than the 60N.
Hot strength:
The epoxy bond compsn is dropped on the stainless steel substrate, load the square silicon chip of 1.5mm, in 120 ℃ baking oven, placed 60 minutes, placement was cured in 60 minutes in 150 ℃ baking oven then.After being cooled to room temperature, above-mentioned stainless steel substrate was placed for 20 seconds being heated on 250 ℃ the hot-plate, under the condition that keeps heating, given the above-mentioned silicon chip application of force to this stainless steel substrate from horizontal direction then, the masterpiece when measuring this silicon chip and peeling off is a hot strength.If hot strength is then for qualified more than the 5N.
Transmittance:
The epoxy bond compsn was placed 60 minutes in 120 ℃ baking oven, then, after placement was cured in 60 minutes in 150 ℃ baking oven, formed the band shape of 15 * 30 * 0.5mm, process the determination of light transmittance sample.This sample is installed among the spectrophotometer U-4001 that makes the Hitachi, measures the transmittance of 460nm.If transmittance is then for qualified more than 80%.
Heat-resisting discolouration:
The size of epoxy bond compsn with 20 * 20 * 0.1mm is printed on the glass substrate, in 120 ℃ baking oven, placed 60 minutes, placement was cured in 60 minutes in 150 ℃ baking oven then.After being cooled to room temperature, measure L with color difference meter
1, a
1, b
1Each value.Then, sample placed 500 hours in 120 ℃ baking oven after, measure L with color difference meter again
2, a
2, b
2Each value.Be worth according to formula by these
Calculate Δ E, when the value less than 5 of Δ E variable color less, be chosen as " zero ", be that 5 variable colors when above are more, be chosen as " * ".In addition, L
1, a
1, b
1And L
2, a
2, b
2Each value is respectively before the heating and the L of heating after 500 hours
*a
*b
*The measured value of color specification system, L representes brightness, a, b represent colourity.
Resistance to ultra violet discoloration:
The size of epoxy bond compsn with 20 * 20 * 0.1mm is printed on the glass substrate, in 120 ℃ baking oven, placed 60 minutes, placement was cured in 60 minutes in 150 ℃ baking oven then.After being cooled to room temperature, measure L with color difference meter
1, a
1, b
1Each value.Then, sample is measured L with color difference meter in irradiation under the UV-lamp that with 365nm is the center after 1 hour again
2, a
2, b
2Each value.Be worth according to formula by these
Calculate Δ E, when the value less than 5 of Δ E variable color less, be chosen as " zero ", be that 5 variable colors when above are more, be chosen as " * ".
Screening characteristics:
The epoxy bond compsn that notes are filled in syringe is that the syringe needle of 0.2mm injects 1000 points continuously from being installed in internal diameter on the injector to inject mouth.At this moment, form coniform or hemispheric be evaluated as " zero ", lead silk and contact with consecutive point, perhaps adjacent point is drawn into wire, and increase to the point more than the 2mm at perhaps coniform angle has more than 3, is evaluated as " * ".
Package stability:
The epoxy bond compsn is sealed in the ointment bottle, 30 ℃ of held 5 days.With the viscosity before and after the viscometer determining placement, the viscosity after the placement is in a ratio of 1.2 times with interior with placing preceding viscosity, is evaluated as " zero ", and the average evaluation above 1.2 times is " * ".
Comprehensive evaluation:
Sample for gained; In the investigation result of cohesive strength, hot strength, reflectivity, heat-resisting discolouration, resistance to ultra violet discoloration, screening characteristics, package stability; Only cohesive strength is that 60N is above, hot strength is that 5N is above, transmittance is 80% or more, heat-resisting discolouration, resistance to ultra violet discoloration, screening characteristics, package stability are " zero "; Comprehensive evaluation is " zero ", and the situation of any one ungratified characteristic is arranged, and is evaluated as " * ".
(embodiment 1～8)
Mix various raw materials according to the wt ratio in the table 1,, prepare the sample of epoxy bond compsn of the present invention through in 3 roll shape mullers, mixing.
Embodiment 1～3rd, in the compsn by the organo-tin compound of the organo-tin compound of epoxy resin (a), silane compound, divalent, 4 valencys, silicon-dioxide that median size is 0.2 μ m, solvent composition; The example that the kind of silane compound is changed; Embodiment 4 is examples that the silica volume among the embodiment 2 is reduced within the scope of the present invention; Embodiment 5 is examples that the silica volume among the embodiment 2 increases within the scope of the present invention; Embodiment 6 is the examples with the amount increase of the organo-tin compound of the silane compound of embodiment 2 and divalent and 4 valencys; Embodiment 7 is the amount minimizings with silane compound, and changes the ratio of divalent and 4 valency organo-tin compounds, and inorganic powder (particle) is near the upper limit of the scope of the invention; And the example that adds additive (a), embodiment 8 are to get into bisphenol f type epoxy resin in the structure when in the composition of embodiment 7, using curing reaction as the example of additive (b).
Gained result one is listed in table 1.In addition, in the tabulation of composition in the table 1, relate to the compsn that mixes composition required in this invention and represent, by contrast, relate to nonessential composition additive (a), additive (b), the parts by weight when representing to be 100 weight parts with composition epoxy resin with weight %.
Table 1
(comparative example 1～9)
Likewise mix each raw material with embodiment 1～8, through in 3 roll shape mullers, mixing, the sample of epoxy bond compsn is relatively used in preparation.The gained evaluation result, with table 1 likewise, one is listed in table 2.
Comparative example 1 is the example that the organo-tin compound among the embodiment 2 is replaced with organo-aluminium compound, and comparative example 2 is the examples that the organo-tin compound among the embodiment 2 replaced with organic zirconate.
Comparative example 3 is to use curing system, and mixes the example that median size is the silicon-dioxide of 0.2 μ m therein, and this curing system adopts known alicyclic epoxy resin and anhydride curing agent and curing catalysts.
Comparative example 4 is the SiO 2 powders that do not use among the embodiment 2, and uses the example of lighttight cupric oxide powder.
The median size that it is difficult that comparative example 5 is to use photopermeability is the example that the SiO 2 powder of 3.1 μ m replaces the SiO 2 powder among the embodiment 2.
Comparative example 6 is the examples that the epoxy resin composition among the embodiment 2 replaced with non-ester ring type bisphenol A type epoxy resin.
Comparative example 7 is to use the curing system that contains bisphenol A type epoxy resin, anhydride curing agent and catalyzer, and mixes the example of light transmission SiO 2 powder.
Comparative example 8 is the examples when only using the divalent organo-tin compound as organometallic compound.
Comparative example 9 is the examples when only using 4 valency organo-tin compounds as organometallic compound.
Table 2
" estimate and investigate "
Can know from table 1; The epoxy bond compsn of embodiment 1～8 is good as the cohesive force of sticker; Can obtain following cured article, this cured article is not only short wavelength's transmittance, to heat, ultraviolet deterioration, discolouration, and screening characteristics, package stability are all good.
On the other hand, comparative example 1 is to use the situation of organo-aluminium compound, though its cohesive strength, hot strength, transmittance, heat-resisting discolouration and resistance to ultra violet discoloration, screening characteristics are good, package stability is relatively poor, and comprehensive evaluation is " * ".
Comparative example 2 is to use the situation of organic zirconate, and is same with comparative example 1, though its cohesive strength, hot strength, transmittance, heat-resisting discolouration and resistance to ultra violet discoloration, screening characteristics are good, package stability is relatively poor, and comprehensive evaluation is " * ".
Comparative example 3 uses the situation of acid anhydrides and curing catalysts as known curing agent component; Though its cohesive strength, hot strength, transmittance, heat-resisting discolouration and resistance to ultra violet discoloration, screening characteristics are out of question; But package stability is relatively poor, and comprehensive evaluation is " * ".
Comparative example 4 is to use the example of lighttight cupric oxide as mineral filler.The color of cured article also becomes black in this example, and it is very low that transmittance becomes.And, though heat-resisting discolouration and resistance to ultra violet discoloration are " zero ", think that this is because original just be black, even thereby resinous principle variable color, also showy cause so easily.
It is the example of the silicon-dioxide of 3.1 μ m as mineral filler that comparative example 5 is to use median size.Because median size is bigger, thereby transmittance is very low.
Comparative example 6 is the examples with the not preferred non-ester ring type bisphenol A type epoxy resin of epoxy resin composition alternative costs inventions, its cohesive strength a little less than, resistance to ultra violet discoloration is relatively poor, comprehensive evaluation is " * ".The weak reason of cohesive strength is considered to, compare with using alicyclic epoxy resin, though can obtain cured article, curing reaction carry out incomplete cause.
Comparative example 7 is same with comparative example 6, is the example that adopts bisphenol A type epoxy resin, anhydride curing agent and curing catalysts.Curing reaction has carried out fully; Thereby obtained enough cohesive strengths and hot strength, but owing to contain the bisphenol A type epoxy resin with phenyl ring, so resistance to ultra violet discoloration is relatively poor; And; Because used anhydride curing agent and curing catalysts, so package stability is relatively poor, comprehensive evaluation is " * ".
Comparative example 8 is examples that organo-tin compound only uses the divalent compound, though its cohesive strength, transmittance and discolouration etc. are enough good, because viscosity is 1.5 times of initial value, package stability is relatively poor, so comprehensive evaluation is " * ".
Comparative example 9 is examples that organo-tin compound only uses 4 valency compounds, because solidification value is not high enough under this test conditions, it is not enough to infer that therefore it solidifies, so cohesive strength, hot strength can not reach desired value, comprehensive evaluation is " * ".
Claims (7)
1. epoxy bond compsn; It is the mineral filler (D) that a kind ofly contains alicyclic epoxy compound (A), have the silane compound (B), organo-tin compound (C) and the light transmission that directly are connected the hydrolization group on the Siliciumatom as the epoxy bond compsn that is used for optical semiconductor that must composition; It is characterized in that wherein organo-tin compound (C) is the mixture of organo-tin compound (c2) of organo-tin compound (c1) and 4 valencys of divalent, and; Total amount based on compsn; The content of above-mentioned each composition is that (A) is 30-95 weight %, (B) is 0.1-15 weight %, (c1) is 0.01-5 weight %; (c2) be 0.01-5 weight %, and (D) be 0.1-50 weight %.
2. the described epoxy bond compsn of claim 1 is characterized in that silane compound (B) is the silane compound of nonnitrogenous atom.
3. claim 1 or 2 described epoxy bond compsns is characterized in that silane compound (B) is for containing 2 or 3 alkoxysilane compound containing trialkylsilyl group in molecular structure that carbonatoms is the hydrolization group of 1-3.
4. the described epoxy bond compsn of claim 1 is characterized in that the combined amount of organo-tin compound (c1) with the organo-tin compound (c2) of 4 valencys of divalent, in wt ratio, (c2)/(c1)=1～20.
5. the described epoxy bond compsn of claim 1, the primary particle median size that it is characterized in that mineral filler (D) is below the 3.0 μ m.
6. claim 1 or 5 described epoxy bond compsns, the band-gap energy that it is characterized in that mineral filler (D) is more than the 2.8eV, and specific refractory power is 1.2～1.8.
7. adopt the optical semiconductor that each described epoxy bond compsn makes in the claim 1～6 to use sticker.
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| JP2005323742A JP4802667B2 (en) | 2005-11-08 | 2005-11-08 | Epoxy resin adhesive composition and optical semiconductor adhesive using the same |
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| JP2005323742 | 2005-11-08 |
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| TWI447939B (en) * | 2007-06-15 | 2014-08-01 | Namics Corp | Conductive die attach adhesive for LED |
| JP5748937B2 (en) * | 2008-04-01 | 2015-07-15 | 日立化成株式会社 | Film sealing adhesive for semiconductor sealing and manufacturing method of semiconductor device |
| JP5599561B2 (en) * | 2008-07-22 | 2014-10-01 | 日立化成株式会社 | Thermosetting resin composition, optical semiconductor element mounting substrate using the same, method for producing the same, and optical semiconductor device |
| JP5550230B2 (en) * | 2008-07-22 | 2014-07-16 | 日立化成株式会社 | Thermosetting resin composition, optical semiconductor element mounting substrate using the same, method for producing the same, and optical semiconductor device |
| US8692394B2 (en) * | 2009-09-30 | 2014-04-08 | Sekisui Chemical Co., Ltd. | Adhesive for semiconductor bonding, adhesive film for semiconductor bonding, method for mounting semiconductor chip, and semiconductor device |
| JP5544843B2 (en) * | 2009-11-27 | 2014-07-09 | 住友金属鉱山株式会社 | Epoxy resin adhesive composition and optical semiconductor adhesive using the same |
| JP5555038B2 (en) * | 2010-04-13 | 2014-07-23 | デクセリアルズ株式会社 | Light-reflective anisotropic conductive adhesive and light-emitting device |
| JP2014162885A (en) * | 2013-02-27 | 2014-09-08 | Sumitomo Metal Mining Co Ltd | Semiconductor element adhesion silicone resin composition and silicon-containing cured product using the same |
| WO2016052664A1 (en) * | 2014-10-01 | 2016-04-07 | ナミックス株式会社 | Resin composition |
| TWI725131B (en) | 2016-03-10 | 2021-04-21 | 日商積水化學工業股份有限公司 | Adhesive for mounting semiconductor sensor chip and semiconductor sensor |
| CN107400491A (en) * | 2017-07-19 | 2017-11-28 | 中山市东溢新材料有限公司 | A kind of transparent epoxy adhesive and its application |
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| JPH083452A (en) * | 1994-06-17 | 1996-01-09 | Kansai Paint Co Ltd | Thermosetting composition and method for curing it |
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| JP2005093724A (en) * | 2003-09-17 | 2005-04-07 | Tokuyama Corp | Primer composition for sealing light emitting diode |
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| JP昭54-127458A 1979.10.03 |
| JP特开2004-256603A 2004.09.16 |
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