CN102985458A - Method for producing cured product and cured product - Google Patents
Method for producing cured product and cured product Download PDFInfo
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- CN102985458A CN102985458A CN2011800336021A CN201180033602A CN102985458A CN 102985458 A CN102985458 A CN 102985458A CN 2011800336021 A CN2011800336021 A CN 2011800336021A CN 201180033602 A CN201180033602 A CN 201180033602A CN 102985458 A CN102985458 A CN 102985458A
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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
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
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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
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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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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- Polymers & Plastics (AREA)
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- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Provided is a method that is for producing a cured product and that is characterized by curing a curable epoxy resin composition, which contains an alicyclic epoxy compound (A) as a curable component, a curing agent (B), and a curing accelerator (C), the amount of the alicyclic epoxy compound (A) contained being at least 60 wt% of the total quantity of the curable component, said curing taking place in curing conditions that are a temperature between 95 DEG C and 135 DEG C inclusive and a time of at least 4.5 hours. As a result of this method of production, by means of optimizing the temperature and time in the curing conditions, it is possible to form a cured product having superior transparency and, for example when used as a sealing material of an optical semiconductor device, having excellent light resistance and cracking resistance in a heat cycle test.
Description
Technical field
The present invention relates to manufacture method and the cured article of cured article, the optical semiconductor device that contains the sealing material of this cured article and contain the sealing material.
Background technology
To the sealing material of the resin, the particularly photosemiconductor that are used for optical semiconductor device, the anti-Fractured of the excellence in the optical transmittance of having relatively high expectations, luminous intensity conservation rate and the thermal cycling test.At present, can realize higher optical transmittance, luminous intensity conservation rate by cycloaliphatic epoxy resin, but have the problem that in thermal cycling test, produces easily the crack.In order to address this problem, adopt following methods: use curing catalysts, solidification value also is divided into some steps, the method that is cured interimly; The method of in cycloaliphatic epoxy resin, mixing bisphenol A type epoxy resin with aromatic ring etc.But, the former method exist operability poor, can not obtain fully anti-broken up shortcoming, there is the shortcoming that results from aromatic ring and cause the luminous intensity conservation rate to reduce in the latter's method.
In patent documentation 1, record a kind of cured article, this cured article is to form by following composition is solidified, described composition contains: curing catalysts, also contain following both as Resins, epoxy: by 3,4-epoxy group(ing) cyclohexenyl methyl-3 ', the cycloaliphatic epoxy resin that 4 '-epoxy group(ing) cyclohexene carboxylate ester consists of, and by 1 of two (the hydroxymethyl)-n-butyl alcohols of 2 ' 2-, the cycloaliphatic epoxy resin that 2-epoxy group(ing)-4-(2-epoxy ethyl) hexanaphthene affixture consists of, simultaneously, contain following formula (A) or (B) in the compound of expression one of at least, making it is 0.01 quality % ~ 1 quality % with respect to above-mentioned light transmission sealing material total mass.This cured article 120 ℃, 1 hour, under 150 ℃, 1 hour condition, be cured subsequently, anti-Fractured is poor.
[Chemical formula 1]
(in the formula, n represents 12 ~ 18 integer, and x+y represents 1 ~ 10 integer.）
(in the formula, n represent 8 or 9, m represent 2 ~ 15 integer.）
Record a kind of Resins, epoxy in patent documentation 2, it uses acid anhydride type curing agent and curing catalyst to carry out thermofixation as the bisphenol A diglycidyl ether of Resins, epoxy.In patent documentation 2, record: reduce in wish in the situation of internal stress of cured article, preferably about 80 ℃ ~ 130 ℃, under the condition about 0.5 hour ~ 5 hours, carry out front curing, then, about 130 ℃ ~ 180 ℃, under the condition about 0.1 hour ~ 15 hours, carry out after fixing, in an embodiment, by after 120 ℃, 1 hour front curing, make cured article at 150 ℃, 3 hours after fixing, under such condition, the anti-Fractured of the cured article that obtains is poor.In addition, in above-mentioned Resins, epoxy, thickness is in the situation of 5mm, and the yellowness index after thermal treatment in 150 ℃, 5 days has increased by 15.2, observes hot xanthochromia.
The prior art document
Patent documentation
Patent documentation 1: No. 4366934 communique of patent
Patent documentation 2: TOHKEMY 2008-179733 communique
Summary of the invention
The problem to be solved in the present invention
The object of the invention is to, the curing of cured article is provided, described cured article is the transparency, photostabilization (luminous intensity retentivity etc.) is excellent and the cured article of the anti-Fractured excellence in thermal cycling test, and as suitable such as the sealing material of optical semiconductor device etc.
Other purpose of the present invention is, cured article is provided, and it solidifies by this curing, its transparency, excellent in light-resistance, and the anti-Fractured in thermal cycling test is excellent.
In addition, other purpose of the present invention is, provides to contain sealing material and optical semiconductor device this cured article, the transparency, excellent in light-resistance and the anti-Fractured excellence in thermal cycling test.
The method of dealing with problems
The inventor etc. concentrate on studies in order to address the above problem, found that: be in the curable resin composition of the solidifying agent such as alicyclic epoxide compound, acid anhydrides more than 60 % by weight and the curing catalyst situation about being cured containing with respect to solidified nature composition total amount, can obtain cured article, sealing material and the optical semiconductor device of the transparency, excellent in light-resistance and the anti-Fractured excellence in thermal cycling test, thereby finish the present invention.
Namely, the invention provides the manufacture method of cured article, it comprises: be more than 95 ℃ and below 135 ℃ and under the condition of cure more than 4.5 hours in temperature, curable epoxy resin composition is cured, described curable epoxy resin composition contains as the alicyclic epoxide compound of solidified nature composition (A), solidifying agent (B) and curing catalyst (C), with respect to solidified nature composition total amount, the content of this alicyclic epoxide compound (A) is more than 60 % by weight.
In addition, the invention provides cured article, it is to make by the manufacture method of above-mentioned cured article.
In addition, the invention provides sealing material, it contains above-mentioned cured article.
And, the invention provides optical semiconductor device, it contains above-mentioned sealing material.
The invention effect
Manufacture method according to cured article of the present invention, by temperature, the time of condition of cure are carried out optimization, it is excellent to obtain the transparency, and in the situation as for example sealing material of optical semiconductor device, its excellent in light-resistance, cured article, sealing material and the semiconductor device of the anti-Fractured excellence in thermal cycling test.
Embodiment
The manufacture method of＜cured article＞
The manufacture method of cured article of the present invention, it comprises: be more than 95 ℃ and below 135 ℃ and under the condition of cure more than 4.5 hours in temperature, curable epoxy resin composition is cured, described curable epoxy resin composition contains as the alicyclic epoxide compound of solidified nature composition (A), solidifying agent (B) and curing catalyst (C), with respect to solidified nature composition total amount, the content of this alicyclic epoxide compound (A) is more than 60 % by weight.
＜condition of cure＞
In the manufacture method of cured article of the present invention, be more than 95 ℃ and below 135 ℃ and under the condition of cure more than 4.5 hours in temperature, curable epoxy resin composition is cured.In this specification sheets, curing can by curable epoxy resin composition for example being put into the mould of appointment or not put into the mould of appointment, be carried out in assigned temperature, mounting fixed time.With regard to curing, can not set interval and carry out constantly the fixed time, also can set interval halfway.Situation about setting interval refers to set time: before and after the timed interval, in total time of the set time that assigned temperature is processed.
Solidification value is temperature more than 95 ℃ and below 135 ℃, and is preferred more than 100 ℃ and be lower than 130 ℃, more preferably more than 100 ℃ and below 120 ℃.Solidification value gets final product in the said temperature scope, can for constant, also can be different various temperature.The above-mentioned timed interval refers to: temperature becomes the time of the temperature that is lower than 95 ℃, can be near room temperature (for example about 25 ℃).Can in this timed interval, curable epoxy resin composition be taken off from mould, the described curable epoxy resin composition that takes off from mould further is cured in above-mentioned solidification value.Solidification value can for constant, also can change more than 95 ℃ and in the scope below 135 ℃ in temperature.Wherein, lifetime interval no matter whether, solidification value is preferably constant.
Be (for example more than 4.5 hours and below 24 hours) more than 4.5 hours set time, is preferably more than 5 hours and below 20 hours, more preferably more than 5 hours and below 16 hours.The timed interval can be set to more than 30 minutes (for example more than 30 minutes ~ 30 days).As the timed interval, preferred 30 minutes ~ 10 days, further preferred 30 minutes ~ 3 days.Situation about setting interval, for example, curable epoxy resin composition can be put into the mould of appointment, under the temperature of appointment, solidified 1 hour ~ 2 hours, then curable epoxy resin composition is let cool near room temperature, take out from mould subsequently, then carry out the curing of remaining time in the temperature of appointment.In the manufacture method of cured article of the present invention, by under above-mentioned condition of cure, curable epoxy resin composition being cured, can obtain the cured article of the anti-Fractured excellence in thermal cycling test.
＜curable epoxy resin composition＞
The curable epoxy resin composition that uses in the manufacture method of cured article of the present invention, contain alicyclic epoxide compound (A), solidifying agent (B) and curing catalyst (C) as the solidified nature composition, the content of this alicyclic epoxide compound (A) is more than 60 % by weight with respect to solidified nature composition total amount.
＜alicyclic epoxide compound (A)＞
As the alicyclic epoxide compound that uses among the present invention (A), get final product so long as have the compound of aliphatics ring, be not particularly limited, be preferably (i) have by the compound of adjacent 2 carbon atoms that consist of alicyclic ring and the epoxy group(ing) that Sauerstoffatom consists of, and (ii) epoxy group(ing) with the compound of singly-bound Direct Bonding on alicyclic ring.
Have compound by adjacent 2 carbon atoms that consist of alicyclic ring and the epoxy group(ing) that Sauerstoffatom consists of as (i), can be from known compound commonly used choice for use at random.As the alicyclic ring epoxy group(ing), preferred epoxycyclohexyl.
Have compound by adjacent 2 carbon atoms that consist of alicyclic ring and the epoxy group(ing) that Sauerstoffatom consists of as (i), from the transparency, stable on heating viewpoint, the cycloaliphatic epoxy resin of following formula (I) expression particularly preferably.
[Chemical formula 2]
In the formula (I), X represents linking group (the divalent group with the atom more than 1), can enumerate such as the group that singly-bound, divalent alkyl, carbonyl, ehter bond, ester bond, carbonate group, amide group and a plurality of above-mentioned group are formed by connecting etc.
As the divalent alkyl, can enumerate carbonatoms and be 1 ~ 18 straight chain shape or a chain alkylidene group, divalent alicyclic alkyl etc.Be 1 ~ 18 straight chain shape or a chain alkylidene group as carbonatoms, can enumerate such as methylene radical, methyl methylene radical, dimethylated methylene base, ethylidene, propylidene, trimethylene etc.As the divalent alicyclic alkyl, for example can enumerate: 1,2-cyclopentylidene, 1,3-cyclopentylidene, cyclopentylidene, 1,2-cyclohexylidene, 1, the divalent cycloalkylidenes such as 3-cyclohexylidene, Isosorbide-5-Nitrae-cyclohexylidene, cyclohexylidene (containing the cycloalkanes fork) etc.
As concatenating group X, preferably contain the linking group of Sauerstoffatom, particularly, can enumerate :-CO-,-O-CO-O-,-COO-,-O-,-CONH-; The group that a plurality of above-mentioned groups are formed by connecting; The group that above-mentioned group more than 1 or 2 and the divalent alkyl more than 1 or 2 are formed by connecting etc.As the divalent alkyl, can enumerate above-mentioned group.
As the typical example of the alicyclic epoxide compound of formula (I) expression, can enumerate: the compound of following formula (I-1) ~ (I-8) expression etc.Also can use commercially available products such as CEL2021P, CEL2081 (manufacturing of Daicel chemical industry).Need to prove that in following formula, l, m represent 1 ~ 30 integer.R is that carbonatoms is 1 ~ 8 alkylidene group, can enumerate: methylene radical, ethylidene, propylidene, isopropylidene, butylidene, isobutylene, sec.-butylidene, pentylidene, hexylidene, inferior heptyl, straight chain shape or a chain alkylidene group such as octylene.Wherein, the carbonatomss such as preferred methylene radical, ethylidene, propylidene, isopropylidene are 1 ~ 3 straight chain shape or a chain alkylidene group.
[chemical formula 3]
With the compound of singly-bound Direct Bonding on alicyclic ring, can enumerate for example compound of following formula (II) expression as (ii) epoxy group(ing).
[chemical formula 4]
In the formula (II), R ' is for having removed the group of p-OH from p unit alcohol; P, n represent natural number.As p unit alcohol R '-(OH)
p, can enumerate: 2 ' 2-two (hydroxymethyl)-(carbonatoms are 1 ~ 15 alcohol etc.) such as the polyvalent alcohols such as n-butyl alcohol.P is preferred 1 ~ 6, and n preferred 1 ~ 30.P is in the situation more than 2, and the n in the group in each " () " can be identical or different.As above-claimed cpd, particularly, can enumerate: 1 of 2 ' 2-two (hydroxymethyl)-n-butyl alcohol, 2-epoxy group(ing)-4-(2-epoxy ethyl) hexanaphthene affixture, EHPE3150 (manufacturing of Daicel chemical industry) etc.
As alicyclic epoxide compound (A), can use separately or be used in combination more than 2 kinds above-mentioned illustrative compound, can preferably use commercially available products such as CEL2021P, CEL2081, EHPE3150 (manufacturing of Daicel chemical industry).
With respect to solidified nature composition total amount contained in the curable epoxy resin composition, the content of alicyclic epoxide compound (A) is 60 % by weight above (for example 60 ~ 100 % by weight).The solidified nature compound of solidified nature composition for being cured by heat or radioactive rays.With respect to the total amount of solidified nature composition, the content of alicyclic epoxide compound (A) can be preferably set to 70 % by weight (70 ~ 100 % by weight), further is preferably set to 80 % by weight above (80 ~ 100 % by weight).Need to prove that in the situation of using alicyclic epoxide compound (A) more than 2 kinds, above-mentioned content is its total content.Be set as above-mentioned scope by the content with alicyclic epoxide compound (A), in the situation that curable epoxy resin composition is cured, can obtain the cured article of optical transmittance and luminous intensity conservation rate excellence.
The total content of the solidified nature composition in the curable epoxy resin composition that uses in the manufacture method of cured article of the present invention is for example 30 ~ 90 % by weight, preferred 40 ~ 80 % by weight, further preferred 40 ~ 70 % by weight.Be set as above-mentioned scope by the content with the solidified nature composition in the curable epoxy resin composition, can obtain the resin combination of solidified nature excellence.
In addition solidified nature composition of＜alicyclic epoxide compound (A)＞
The curable epoxy resin composition that uses among the present invention can contain alicyclic epoxide compound (A) epoxy compounds in addition.As alicyclic epoxide compound (A) epoxy compounds in addition, also can use by at the epoxy group(ing) di-2-ethylhexyl hexahy-, two (2-ethylhexyl) esters of epoxy group(ing) hexahydrophthalic acid, 1, the 4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, the triglycidyl ether of glycerine, the triglycidyl ether of TriMethylolPropane(TMP), four glycidyl ethers of Sorbitol Powder, six glycidyl ethers of Dipentaerythritol, the diglycidylether of polyoxyethylene glycol, the diglycidylether of polypropylene glycol, at propylene glycol, the one kind or two or more epoxide of addition on the aliphatic polyols such as glycerine and the polyglycidyl ether of the polyether glycol that obtains, monoglycidyl ether or the phenol of aliphatic long-chain diprotic acid aliphatics higher alcohols, cresols, butylphenol, or the monoglycidyl ether of the Aethoxy Sklerol that obtains by addition epoxide on above-mentioned substance, the glycidyl esters of higher fatty acid, epoxidised soybean oil, the epoxy group(ing) octyl stearate, the epoxy group(ing) butyl stearate, the epoxidation linseed oil, epoxidized polybutadiene, oxyethane, propylene oxide, Styrene epoxide, methyl glycidyl ether, butylglycidyl ether, glycidyl allyl ether, phenyl glycidyl ether, ethylene glycol glycidyl phenylate, the ethylene glycol benzyl glycidyl ether, Diethylene Glycol glycidyl THP trtrahydropyranyl ether, glycidyl methacrylate, glycidyl ester ether etc., or the material that replaced by fluorine of the part or all of hydrogen atom of above-mentioned epoxy compounds.
In addition, apart from the above, also can use inside to have the oligomeric radiation-curable resin of epoxy group(ing).Can enumerate such as epoxidized polybutadiene (ProductName: EPL PB3600, PB4700, Daisel chemical industry Co., Ltd), epoxidation vinyl benzene butadiene block copolymer (ProductName: Epofriend AT501, Daisel chemical industry Co., Ltd) etc.In addition, phenolic resin varnish type epoxy resin is arranged, for example so that phenol, cresols, the phenols such as halogenated phenol and alkylphenol and formaldehyde react under an acidic catalyst and the phenolic varnish class that obtains, further react resulting material (ProductName: EOCN-103 with epoxy chloropropane and/or methyl epichlorohydrin, EOCN-104S, EOCN-1020, EOCN-1027, EPPN-201, BREN-S, Nippon Kayaku K. K, ProductName: DEN-431, DEN-439, Dow Chemical, and ProductName: N-73, VH-4150, Dainippon Ink. ﹠ Chemicals Inc) etc.In addition, bisphenols and the resulting bisphenol-type epoxy resins of epichlorohydrin reaction such as making dihydroxyphenyl propane, Bisphenol F, bisphenol S and tetrabromo-bisphenol are arranged or make the diglycidylether of dihydroxyphenyl propane and the condenses of above-mentioned bisphenols and resulting bisphenol-type epoxy resin of epichlorohydrin reaction (ProductName: EPIKOTE1004, EPIKOTE1002, oiling SHELL Co., Ltd., ProductName: DER-330, DER-337, Dow Chemical) etc.
As alicyclic epoxide compound (A) epoxy compounds in addition, can use separately above-mentioned illustrative compound or be used in combination more than 2 kinds.As alicyclic epoxide compound (A) epoxy compounds in addition, can preferably use bisphenol A type epoxy resin etc. to have the epoxy compounds of aromatic ring.Also can not use alicyclic epoxide compound (A) epoxy compounds in addition.
＜solidifying agent (B)＞
The curable epoxy resin composition that uses in the manufacture method of cured article of the present invention contains solidifying agent (B).Solidifying agent (B) has so that have the effect that the compound of epoxy group(ing) is cured.As the solidifying agent among the present invention (B), can use known solidifying agent as hardener for epoxy resin commonly used.As the solidifying agent among the present invention (B), wherein, be preferably at 25 ℃ and be liquid acid anhydrides, can enumerate such as methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenylsuccinic anhydride, methyl Nadic anhydride etc.In addition, can in the acid anhydrides of normal temperature (25 ℃) for liquid state, make liquid mixture with being dissolved in for the acid anhydrides of solid state at normal temperature (25 ℃) such as Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, tetrahydrotoluene dicarboxylic anhydride etc., it is used as the solidifying agent among the present invention (B).In addition, in the present invention, as solidifying agent (B), also can use the commercially available products such as RIKACID MH-700 (new Japanese physics and chemistry manufacturing), HN-5500 (Hitachi changes into manufacturing).
Solidifying agent (B) can for a kind of, also can select two or more the mixing with arbitrary proportion to use.Total amount 100 weight parts with respect to the compound with epoxy group(ing) contained in the curable epoxy resin composition, the consumption of solidifying agent (B) for example is 50 ~ 150 weight parts, preferred 100 ~ 145 weight parts, more specifically, for the per 1 equivalent epoxy group(ing) in contained whole compounds with epoxy group(ing) in the above-mentioned curable epoxy resin composition, preferably use with the ratio of 0.5 ~ 1.5 equivalent.When the consumption of solidifying agent (B) is lower than 50 weight part, might effect become insufficient, the tenacity of cured article reduces, and on the other hand, when the consumption of solidifying agent (B) was higher than 150 weight part, cured article was painted and form and aspect worsen sometimes.Need to prove that in the situation of using solidifying agent (B) more than 2 kinds, above-mentioned consumption is its total consumption.
In the present invention, for the per 1 equivalent epoxy group(ing) in contained whole compounds with epoxy group(ing) in the curable epoxy resin composition, preferably use solidifying agent (B) with the ratio of 0.5 ~ 1.5 equivalent, therefore, the reflecting point during curing is many, thinks in addition, owing to be more than 95 ℃ and under the low temperature below 135 ℃ curable epoxy resin composition to be cured in temperature, therefore, stable and be cured equably, can be manufactured on the cured article of the anti-Fractured excellence in the thermal cycling test.
＜curing catalyst (C)＞
The curable epoxy resin composition that uses in the manufacture method of cured article of the present invention contains curing catalyst (C).Curing catalyst (C) refers to when by solidifying agent the compound with epoxy group(ing) being cured, to have the compound of the function that promotes curing speed.As the curing catalyst (C) that can in curable epoxy resin composition of the present invention, contain, can use known curing catalyst commonly used, for example can enumerate: 1,8-diazabicyclo [5.4.0], 11 carbon-7-alkene (DBU) and salt thereof (for example, phenolate, octyl group hydrochlorate, tosilate, formate, tetraphenyl boric acid ester salt); 1,5-diazabicyclo ［ 4.3.0 ］ ninth of the ten Heavenly Stems-5-alkene (DBN) and salt thereof are (for example
Salt, sulfonium salt, quaternary ammonium salt, iodine
Salt); Benzyl dimethyl amine, 2,4,6-three (dimethylaminomethyl) phenol, N, the tertiary amines such as N-dimethylcyclohexylamine; The imidazoles such as 2-ethyl-4-methylimidazole, 1-cyano ethyl-2-ethyl-4-methylimidazole; The phosphine such as phosphoric acid ester, triphenylphosphine class; Tetraphenyl
Four (p-methylphenyl) borate etc.
Compound; The organic metal salts such as octyl group acid tin, octyl group acid zinc; Metal complex etc.These materials can use separately or mix more than 2 kinds and use.
In addition, in the present invention, as curing catalyst (C), also can use the commercially available products such as U-CAT SA506, U-CAT SA102, U-CAT5003, U-CAT18X, 12XD (exploitation product) (being San-apro makes), TPP-K, TPP-MK (be northern Xinghua and learn industry manufacturing), PX-4ET (Japan Chemical Industry manufacturing).
Curing catalyst (C) can for a kind of, also can be use mixing two or more with arbitrary proportion.With respect to total amount 100 weight parts of the compound with epoxy group(ing) contained in the curable epoxy resin composition, its consumption for example be 0.05 ~ 5 weight part, preferred 0.1 ~ 3 weight part, particularly preferably 0.2 ~ 3 weight part, most preferably about 0.25 ~ 2.5 weight part.When the consumption of curing catalyst (C) was lower than 0.05 weight part, it was insufficient sometimes to solidify facilitation effect, and on the other hand, when the consumption of curing catalyst (C) was higher than 5 weight part, cured article was painted and form and aspect worsen sometimes.Need to prove that in the situation of using curing catalyst (C) more than 2 kinds, above-mentioned consumption is its total consumption.
＜mineral filler＞
The curable epoxy resin composition that uses in the manufacture method of cured article of the present invention can further contain mineral filler.As mineral filler, be not particularly limited, can use in silicon-dioxide, aluminum oxide, mica, synthetic mica, talcum, calcium oxide, calcium carbonate, zirconium white, titanium oxide, barium titanate, kaolin, wilkinite, diatomite, boron nitride, aluminium nitride, silicon carbide, zinc oxide, cerium oxide, Cs2O, magnesium oxide, granulated glass sphere, glass fibre, graphite, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, the Mierocrystalline cellulose etc. more than a kind.In addition, as mineral filler, can enumerate nano silicon, nano-titanium oxide, nano zircite, carbon nanotube etc.
These mineral fillers can use the flame hydrolysis or the known methods such as flame thermal decomposition method, plasma method that disclose in No. 96/31572 record such as the world to make.As preferred mineral filler, can use the nano-dispersed colloidal sol class of stabilized colloidal inorganic particulate etc., as commercially available product, can obtain the silicon dioxide gel of BAYER company manufacturing, the SnO that Goldschmidt company makes
2The TiO that colloidal sol class, MERCK company make
2The SiO that colloidal sol class, Nissan Chemicals company make
2, ZrO
2, A1
2O
3And Sb
2O
3The commercially available products such as Aerosil dispersion class that colloidal sol or DEGUSSA company make.
Mineral filler can change by the modification on surface its viscosity behavior.The surface modification of particle can use known surface-modifying agent to carry out.As this surface-modifying agent, can use such as can form with the functional group on the surface that is present in mineral filler the interactional compound such as covalent linkage or complexing and can with the interactional compound of polymeric matrix.As this surface-modifying agent, can use such as the compound that has the functional groups such as carboxyl, (primary, secondary, uncle) amino, quaternary ammonium group, carbonyl, glycidyl, vinyl, (methyl) acryloxy, sulfydryl in the molecule etc.As this surface-modifying agent, be liquid usually under standard temperature and pressure condition, by intramolecular carbonatoms for for example below 15, preferred below 10, particularly preferably the low-molecular-weight organic compound below 8 consists of.The molecular weight of above-mentioned low-molecular-weight organic compound for example is below 500, and is preferred below 350, is in particular below 200.
As preferred surface-modifying agent, can enumerate such as: carbonatomss such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, vinylformic acid, methacrylic acid, β-crotonic acid, citric acid, hexanodioic acid, succsinic acid, pentanedioic acid, oxalic acid, toxilic acid and fumaric acid is 1 ~ 12 saturated or unsaturated list and polycarboxylic acid (preferred monocarboxylic acid class); And the ester class (C such as preferable methyl methyl acrylate
1~ C
4Alkyl esters); Amides; Methyl ethyl diketone, 2 ' 4-hexanedione, 3,5-heptadione, etheric acid and C
1~ C
4The beta-dicarbonyl compounds such as alkyl etheric acid class etc.In addition, be not particularly limited, also can use known silane coupling agent commonly used as surface-modifying agent.
The particle diameter of mineral filler is generally about 0.01nm ~ 200 μ m, and preferred 0.1nm ~ 100 μ m is in particular about 0.1nm ~ 50 μ m.
When the total content of solidified nature composition was set as 100 weight part, the content of mineral filler was preferably 1 ~ 2000 weight part, more preferably 10 ~ 1000 weight parts.In addition, with respect to the total amount of curable epoxy resin composition, the content of mineral filler for example is 5 ~ 95 % by weight, preferred 10 ~ 90 % by weight.Need to prove that in the situation of using mineral filler more than 2 kinds, above-mentioned content is its total content.
＜rubber particles＞
Can contain rubber particles in the curable epoxy resin composition that uses in the present invention.As rubber particles, can enumerate such as particle shape NBR (acrylonitrile-butadiene rubber), reactive terminal carboxyl NBR (CTBN), not containing metal NBR, particle shape SBR (styrene butadiene rubbers) etc.Rubber particles has following structure: by the core segment with caoutchouc elasticity with coat the multilayered structure (core shell structure) that at least 1 layer of shell of this core segment consists of, the surface have as can with hydroxyl and/or the carboxyl of the functional group of cycloaliphatic epoxy resin reaction, it is that 10nm ~ 500nm, maximum particle diameter are the rubber particles of 50nm ~ 1000nm for median size, can be that the specific refractivity of cured article of the specific refractory power of this rubber particles and this curable epoxy resin composition is for ± 0.02 with interior rubber particles.Rubber particles can be for a kind of, also can be use mixing two or more with ratio arbitrarily.With respect to total 100 weight parts of solidified nature composition, the content of rubber particles for example is 0.5 ~ 30 weight part, preferred 1 ~ 20 weight part, further preferred 1 ~ 10 weight part.When use level is lower than 0.5 weight part, might reduce by anti-Fractured, when it is higher than 30 weight part, might thermotolerance and transparency reduction.Need to prove that in the situation of using rubber particles more than 2 kinds, above-mentioned content is its total content.
＜additive＞
Apart from the above, curable epoxy resin composition of the present invention can use various additives in the scope of not damaging effect of the present invention.The compound that use such as ethylene glycol, Diethylene Glycol, propylene glycol, glycerine etc. have a hydroxyl can make sluggish ground carry out during as additive.In addition, in the scope of not damaging viscosity or the transparency, can use silane coupling agent, tensio-active agent, fire retardant, tinting material, antioxidant, UV light absorber, ionic adsorption body, pigment, fluor, the releasing agents etc. such as polysiloxane-based and fluorine defoamer, flow agent, γ-glycidoxypropyltrime,hoxysilane additive commonly used.
The curable epoxy resin composition that uses in the manufacture method of cured article of the present invention obtains by above-mentioned each homogeneous chemical composition ground is mixed.In order to obtain above-mentioned curable epoxy resin composition, preferred use rotation-revolution formula churning deaerator, clarifixator, planetary-type mixer, 3 roller mills, ball mill etc. usually known mixing with machine stir, dissolve, mixing, dispersion etc., make as much as possible each composition become even.
＜cured article＞
In the present invention, by under above-mentioned condition of cure, above-mentioned curable epoxy resin composition is solidified, can obtain the transparency, photostabilization (luminous intensity retentivity etc.) is excellent and the cured article of the various physical properties excellent such as anti-Fractured in thermal cycling test.
＜sealing material＞
Sealing material of the present invention is by being used as sealing agent with above-mentioned curable epoxy resin composition, and under above-mentioned condition of cure, make its curing, its transparency, photostabilization (luminous intensity retentivity etc.) excellence, and the various physical properties excellent such as anti-Fractured in thermal cycling test.
＜optical semiconductor device＞
Optical semiconductor device of the present invention is by sealing optical semiconductor with above-mentioned curable epoxy resin composition and its curing being obtained.To the sealing of optical semiconductor, undertaken by following: will inject with the curable epoxy resin composition of aforesaid method preparation in the shaping mould of appointment, under above-mentioned condition of cure, be heating and curing.Optical semiconductor device of the present invention, its transparency, photostabilization (luminous intensity retentivity etc.) excellence, and the various physical properties excellent such as anti-Fractured in thermal cycling test.
According to the manufacture method of cured article of the present invention, can obtain: the transparency, photostabilization (luminous intensity retentivity etc.) excellence, and the optical semiconductor encapsulating material of the various physical properties excellent such as the anti-Fractured in thermal cycling test, adhesives, electrically insulating material, veneer sheet, coating, printing ink, coating, sealing agent, resist, matrix material, the transparent base material, clear sheet, transparent film, optical element, optical lens, optical component, light chisel, Electronic Paper, touch panel, the solar cell basal disc, optical waveguides, light guiding plate, holographic memory etc.
Embodiment
Below, based on embodiment the present invention is done with more detailed description, but the present invention is not limited to these embodiment.
Production Example 1
(Resins, epoxy A agent)
According to the prescription of the cooperation shown in the table 1 (unit: weight part) with 2,1 of two (the hydroxymethyl)-n-butyl alcohols of 2-, 2-epoxy group(ing)-4-(2-epoxy ethyl) hexanaphthene affixture (Daicel chemical industry is made EHPE3150) and 3,4-epoxy group(ing) cyclohexyl methyl-3 ', 4 '-epoxy-cyclohexane carboxylicesters (Daicel chemical industry is made CEL2021P) or bisphenol A type epoxy resin (Nippon Steel's chemistry is made YD-128) mix, stirred 1 hour at 80 ℃, thus, make 2,1 of two (the hydroxymethyl)-n-butyl alcohols of 2-, the dissolving of 2-epoxy group(ing)-4-(2-epoxy ethyl) hexanaphthene affixture obtains Resins, epoxy (mixture).
Production Example 2
(mixture of solidifying agent, curing catalyst and additive, flexible imparting agent below is recited as the B agent)
As the B agent, use from revolution type whipping appts (あ わ と り Practice too youth AR-250THINKY makes), with solidifying agent (the new Japanese physics and chemistry manufacturing RIKACID MH-700 of 100 weight parts; 4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride=70/30), the flexible imparting agent (new Japanese physics and chemistry is made RIKACID HF-08) of the additive (pure pharmaceutical worker already makes ethylene glycol with light) of the curing catalyst (San-apro makes 18X) of 0.5 weight part, 1 weight part, 3 weight parts evenly mixes and carry out deaeration, obtains the B agent.
Embodiment 1 ~ 7, comparative example 1 ~ 7
Weight part), each composition used from revolution type whipping appts (あ わ と り Practice too youth AR-250THINKY makes) mix equably and carry out deaeration the Resins, epoxy A agent that will be obtained by Production Example 1 and the B agent that obtained by Production Example 2 are according to the prescription of the cooperation shown in the table 1 (unit:, obtain curable epoxy resin composition.
Condition of cure (1)
To inject mould (shape: lamp shape, size: Φ 3) by the resin combination that embodiment 1,3 obtains, after insertion is equipped with the lead frame of blue light-emitting diode, in baking oven (ESPEC company make GPHH-201), in 100 ℃, be heating and curing 15 hours, obtain with resin element having been carried out the optical semiconductor device of sealing.
Condition of cure (2)
To be flow into by the resin combination that embodiment 2,4 ~ 7 obtains mould (shape: lamp shape, size: Φ 3), after insertion is equipped with the lead frame of blue light-emitting diode, in baking oven (ESPEC company make GPHH-201), in 120 ℃, be heating and curing 7 hours, obtain with resin element having been carried out the optical semiconductor device of sealing.
Condition of cure (3)
To be flow into by the resin combination that comparative example 1,4 obtains mould (shape: lamp shape, size: Φ 3), after insertion is equipped with the lead frame of blue light-emitting diode, in baking oven (ESPEC company make GPHH-201), in 120 ℃, be heating and curing 4 hours, obtain with resin element having been carried out the optical semiconductor device of sealing.
Condition of cure (4)
To be flow into by the resin combination that comparative example 2,5 ~ 7 obtains mould (shape: lamp shape, size: Φ 3), after insertion is equipped with the lead frame of blue light-emitting diode, in baking oven (ESPEC company make GPHH-201), be heating and curing 2 hours in 100 ℃, thereafter, be heating and curing 3 hours at 140 ℃, obtain thus with the resin that has solidified element having been carried out the optical semiconductor device of sealing.
Condition of cure (5)
To be flow into by the resin combination that comparative example 3 obtains mould (shape: lamp shape, size: Φ 3), after insertion is equipped with the lead frame of blue light-emitting diode, in baking oven (ESPEC company make GPHH-201), in 150 ℃, be heating and curing 7 hours, obtain thus the optical semiconductor device that element has been carried out sealing with the resin that has solidified.
Optical transmittance
Curable epoxy resin composition before the curing that will obtain according to the cooperation prescription of embodiment and comparative example is cast in the mould of appointment, is heating and curing under above-mentioned condition of cure, and making thickness is the plate of 3mm.Use spectrophotometer (Shimadzu Seisakusho Ltd. makes spectrophotometer UV-2450) to measure the optical transmittance of 450nm.Show the result in table 1.
The luminous intensity conservation rate
Use total light flux to measure the total light flux that machine (U.S. Optronic Laborataries company makes many light splitting radioassay OL771 of system) is measured the optical semiconductor device that is obtained by embodiment and comparative example.And, be determined in 23 ℃, the constant temperature and humidity cabinet of 60%RH, in optical semiconductor device, make the electric current of 100mA flow through total light flux after 300 hours.Calculate the luminous intensity conservation rate by following formula.Show the result in table 1.
{ luminous intensity conservation rate (%) }={ total light flux after 300 hours (lm) }/{ 0 hour total light flux (lm) } * 100
Anti-Fractured test
In the optical semiconductor device that is obtained by embodiment and comparative example, use heat impact tester (manufacturing of small-sized cold percussion mechanism TSE-11-A ESPEC company) carry out 400 circulations with-40 ℃ of 15 minutes and 120 ℃ of 15 minutes thermal shock tests as 1 circulation.Thereafter, use digit microscope (VHX-900Keyence manufacturing) to observe the length in crack, computation and measurement is in 5 optical semiconductor devices, and having the fracture length that produces is the number of the optical semiconductor device in the above crack of 90 μ m.Show the result in table 1.
Industrial applicibility
Manufacturing method according to the invention, by with the temperature in the condition of cure, time optimization, it is excellent to form the transparency, in the situation as for example sealing material of optical semiconductor device, and the cured article of photostabilization, the anti-Fractured excellence in thermal cycling test.
Claims (4)
1. the manufacture method of cured article, it comprises:
Be more than 95 ℃ and below 135 ℃ and under the condition of cure more than 4.5 hours in temperature, curable epoxy resin composition is cured, described curable epoxy resin composition contains as the alicyclic epoxide compound of solidified nature composition (A), solidifying agent (B) and curing catalyst (C), with respect to solidified nature composition total amount, the content of this alicyclic epoxide compound (A) is more than 60 % by weight.
2. cured article, it is made by manufacture method claimed in claim 1.
3. sealing material, it contains cured article claimed in claim 2.
4. optical semiconductor device, it contains sealing material claimed in claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-226221 | 2010-10-06 | ||
| JP2010226221A JP2012077257A (en) | 2010-10-06 | 2010-10-06 | Method for producing cured product, and cured product |
| PCT/JP2011/070989 WO2012046552A1 (en) | 2010-10-06 | 2011-09-14 | Method for producing cured product and cured product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102985458A true CN102985458A (en) | 2013-03-20 |
Family
ID=45927549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800336021A Pending CN102985458A (en) | 2010-10-06 | 2011-09-14 | Method for producing cured product and cured product |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2012077257A (en) |
| KR (1) | KR20130118298A (en) |
| CN (1) | CN102985458A (en) |
| TW (1) | TW201217421A (en) |
| WO (1) | WO2012046552A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497486A (en) * | 2014-12-16 | 2015-04-08 | 浙江华正新材料股份有限公司 | Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition |
| CN107216613A (en) * | 2017-07-07 | 2017-09-29 | 东莞市德聚胶接技术有限公司 | Light curing resin composition and preparation method thereof |
| CN111684011A (en) * | 2018-02-08 | 2020-09-18 | 关西涂料株式会社 | Resist composition and resist film |
| CN115124748A (en) * | 2022-07-28 | 2022-09-30 | 海南联塑科技实业有限公司 | Method for inhibiting degradation of plastic and precipitating micro plastic and application |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6119376B2 (en) * | 2013-03-29 | 2017-04-26 | 三菱化学株式会社 | Epoxy resin, epoxy resin composition and cured product |
| TW201502192A (en) * | 2013-06-03 | 2015-01-16 | Daicel Corp | Curable epoxy resin composition |
| JP6401041B2 (en) * | 2014-12-19 | 2018-10-03 | 株式会社ダイセル | Curable epoxy resin composition |
| KR102140259B1 (en) * | 2018-01-11 | 2020-07-31 | 주식회사 엘지화학 | Epoxy resin composition for molding semiconductor, molding film and semiconductor package using the same |
| WO2019139354A1 (en) * | 2018-01-11 | 2019-07-18 | 주식회사 엘지화학 | Epoxy resin composition for semiconductor molding, and molding film and semiconductor package using same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3283606B2 (en) * | 1993-02-17 | 2002-05-20 | 日本化薬株式会社 | Organopolysiloxane and epoxy resin composition containing the same |
| JP3623530B2 (en) * | 1994-04-18 | 2005-02-23 | 日東電工株式会社 | Optical semiconductor device |
| JP2003026763A (en) * | 2001-07-13 | 2003-01-29 | New Japan Chem Co Ltd | Epoxy resin composition |
| JP2007016063A (en) * | 2005-07-05 | 2007-01-25 | San Apro Kk | Epoxy resin composition for sealing semiconductor |
| JP4398500B2 (en) * | 2007-04-06 | 2010-01-13 | 株式会社日本触媒 | Resin composition and optical member |
| JP5154340B2 (en) * | 2008-08-27 | 2013-02-27 | 株式会社ダイセル | Resin composition for optical semiconductor encapsulation |
| JP5606752B2 (en) * | 2010-02-25 | 2014-10-15 | 株式会社ダイセル | Resin composition for optical semiconductor sealing and optical semiconductor device using the same |
-
2010
- 2010-10-06 JP JP2010226221A patent/JP2012077257A/en active Pending
-
2011
- 2011-09-14 WO PCT/JP2011/070989 patent/WO2012046552A1/en active Application Filing
- 2011-09-14 CN CN2011800336021A patent/CN102985458A/en active Pending
- 2011-09-14 KR KR1020137001868A patent/KR20130118298A/en not_active Application Discontinuation
- 2011-09-29 TW TW100135136A patent/TW201217421A/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497486A (en) * | 2014-12-16 | 2015-04-08 | 浙江华正新材料股份有限公司 | Anti-yellowing modified halogen-free white resin composition, laminated board and preparation method of composition |
| CN107216613A (en) * | 2017-07-07 | 2017-09-29 | 东莞市德聚胶接技术有限公司 | Light curing resin composition and preparation method thereof |
| CN111684011A (en) * | 2018-02-08 | 2020-09-18 | 关西涂料株式会社 | Resist composition and resist film |
| CN111684011B (en) * | 2018-02-08 | 2023-09-01 | 关西涂料株式会社 | Resist composition and resist film |
| CN115124748A (en) * | 2022-07-28 | 2022-09-30 | 海南联塑科技实业有限公司 | Method for inhibiting degradation of plastic and precipitating micro plastic and application |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20130118298A (en) | 2013-10-29 |
| JP2012077257A (en) | 2012-04-19 |
| WO2012046552A1 (en) | 2012-04-12 |
| TW201217421A (en) | 2012-05-01 |
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Application publication date: 20130320 |