CN104693419A - Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device - Google Patents
Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device Download PDFInfo
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- CN104693419A CN104693419A CN201510131992.6A CN201510131992A CN104693419A CN 104693419 A CN104693419 A CN 104693419A CN 201510131992 A CN201510131992 A CN 201510131992A CN 104693419 A CN104693419 A CN 104693419A
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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
- C08G59/40—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 curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
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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
- 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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- Condensed Matter Physics & Semiconductors (AREA)
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- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
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Abstract
The invention relates to epoxy resin curing agent, epoxy resin composition, a hardened material thereof, and an optical semiconductor device. The epoxy resin hardening agent contains a multivalent carboxylic acid anhydride and a dendritic molecule with a hydroxy value of 400-500mg KOH/g. The multivalent carboxylic acid anhydride is 4-methylhexahydrophthalic anhydride, or the composition of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride.
Description
The divisional application of the patent application of " epoxy curing agent, composition epoxy resin, its cured article and optical semiconductor device " that the present invention is application number is 2009801299408 (international application no is PCT/JP2009/063188), the applying date, to be July 23, denomination of invention in 2009 be.
Technical field
The present invention relates to epoxy curing agent, composition epoxy resin, its cured article and optical semiconductor device.Further specifically, relate to for the formation of painted less, the epoxy curing agent of the cured article of resistance to cracking and transparency excellence, composition epoxy resin, its cured article and optical semiconductor device.
Background technology
Usually, the epoxy resin cured product obtained by acid anhydrides and epoxy resin, cheap and excellences such as the transparency, electric insulating quality, chemical proofing, wet fastness, cementability, for various uses such as insulating material, semiconductor material, adhesives, coating materials.As a representational use example, the material for sealing of the luminous element for the protection of photodiode (Light-emitting diode: hereinafter referred to as LED) can be enumerated.In recent years, along with the light source and fluor that send short-wavelength light being carried out the universal of the White LED combined, the deterioration of the solid material of encapsulation is regarded as problem.
That is, in the case of white leds, owing to using more high-octane light source, therefore compared to existing redness, green LED, material for sealing deterioration is produced and the problem that easily lifetime that is painted, LED is such.In addition, the miniaturization caused along with the improvement by luminous element and the propelling of big current, when the heat produced when LED long-term lighting is also become large, can cause the deterioration of packaged material thus similarly.
Epoxy resin further universal in, this deterioration caused by light, thermal conductance is suppressed to as important problem.As solving the method for this problem, someone proposes the composition epoxy resin (for example, referring to patent documentation 1,2 and 3) using alicyclic epoxy resin to substitute the easy aromatic epoxy resin because of light, heat and deterioration.
On the other hand, for employing the composition epoxy resin of this alicyclic epoxy resin, have following shortcoming, that is, the conditions such as the cured article obtained lacks obdurability, Yin Wendu change and easily produce crack.In order to solve this problem, as the method making the cured article obtained by composition epoxy resin become tough, there will be a known the technology using and comprise various high molecular properties-correcting agent.Such as, someone proposes: by adding vibrin in composition epoxy resin, thus when not damaging the transparency of cured article, improves the method (for example, referring to patent documentation 4) of obdurability.
But usual vibrin is easily with color when condensation, and in the invention therefore recorded in above-mentioned patent documentation 4, as shown in embodiment, cured article is coloured to yellow to brown significantly.Therefore, such as requiring as above-mentioned LED material for sealing as in water white purposes, there is problem in practical use.
In order to solve such problem, someone proposes the technology (for example, referring to patent documentation 5) of adding dendrimer.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-196151 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-012896 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2003-221490 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2004-131553 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2007-314740 publication
Summary of the invention
The problem that invention will solve
But, for the technology of aforementioned interpolation dendrimer, uprise tendency because mixed viscosity exists, and there is deterioration in the intensity of cured article, therefore there is reluctant problem.Thus, when particularly requiring trickle processing, surface smoothness in the sealing of LED, be unaccommodated.
The present invention develops in view of the above problems, its provide a kind of take into account mixed low viscosity and solidification after intensity and can be formed painted less, the epoxy curing agent of the cured article of resistance to cracking and transparency excellence.In addition, the invention provides low-viscosity epoxy resin combination, painted less, the epoxy resin composition thing of resistance to cracking and transparency excellence and optical semiconductor device.
Solve the technical scheme of problem
The present inventor, conduct in-depth research to solve above-mentioned problem, found that the following fact, thus complete the present invention: adding under the effect be mixed with as the dendritic high molecular epoxy curing agent of certain tree of properties-correcting agent in polybasic acid anhydride, easy acquisition low viscosity and process be easy to composition epoxy resin, in addition, easily obtain painted few, the cured article of intensity, resistance to cracking and transparency excellence.
The present invention relates to following [1] ~ [15].
[1] epoxy curing agent, comprises the dendrimer of below polybasic acid anhydride and hydroxyl value 550mgKOH/g.
[2] according to the epoxy curing agent that [1] is recorded, wherein, the weight-average molecular weight of dendrimer is less than 2000.
[3] according to the epoxy curing agent that [1] or [2] is recorded, wherein, the viscosity of dendrimer at 25 DEG C is below 10Pas.
[4] according to the epoxy curing agent that any one in [1] ~ [3] is recorded, wherein, the compound of polybasic acid anhydride represented by following general formula (1).
[chemical formula 1]
(in formula, R
1~ R
4represent hydrogen atom independently of one another, or the alkyl of the carbonatoms 1 ~ 4 of straight or branched, wherein, be selected from R
1~ R
4in the two also can in conjunction with and form ring.)
[5] according to the epoxy curing agent that any one in [1] ~ [4] is recorded, wherein, dendrimer is polyester.
[6] according to the epoxy curing agent that any one in [1] ~ [5] is recorded, wherein, relative to polybasic acid anhydride 100 weight part, dendrimer 1 ~ 60 weight part is comprised.
[7] composition epoxy resin, comprises the epoxy curing agent that any one in epoxy resin and [1] ~ [6] is recorded.
[8] composition epoxy resin, comprises the dendrimer of below epoxy resin, polybasic acid anhydride and hydroxyl value 550mgKOH/g.
[9] according to the composition epoxy resin that [8] are recorded, wherein, the weight-average molecular weight of dendrimer is less than 2000.
[10] according to the composition epoxy resin that [8] or [9] are recorded, wherein, the viscosity of dendrimer at 25 DEG C is below 10Pas.
[11] according to the composition epoxy resin that any one in [8] ~ [10] is recorded, wherein, the compound of polybasic acid anhydride represented by following general formula (1).
[chemical formula 2]
(in formula, R
1~ R
4represent hydrogen atom independently of one another, or the alkyl of the carbonatoms 1 ~ 4 of straight or branched, wherein, be selected from R
1~ R
4in the two also can in conjunction with and form ring.)
[12] according to the composition epoxy resin that any one in [8] ~ [11] is recorded, wherein, dendrimer is polyester.
[13] according to the composition epoxy resin that any one in [8] ~ [12] is recorded, wherein, relative to polybasic acid anhydride 100 weight part, dendrimer 1 ~ 60 weight part is comprised.
[14] cured article, is formed by the epoxy resin composition making any one in [7] ~ [13] record.
[15] optical semiconductor device, is formed optical semiconductor sealing by the cured article recorded with [14].
With regard to content of the present invention, with No. 2008-194808, the Japanese Patent Application of applying on July 29th, 2008, and the theme recorded in No. 2009-127596, the Japanese Patent Application of application on May 27th, 2009 is associated, their disclosure is quoted in herein with way of reference.
Invention effect
According to the present invention, can obtain the epoxy curing agent forming following composition epoxy resin, described composition epoxy resin is low viscosity after blending and process is easy, and the intensity of cured article is good, thus, can obtain painted less, the cured article of resistance to cracking and transparency excellence.
Embodiment
Below, the present invention is described in detail.
There is no particular restriction for the polybasic acid anhydride used in the present invention, such as, can enumerate: succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methylendomethylene Tetra Hydro Phthalic Anhydride, itaconic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride etc.More than two kinds also can be share by they.
In order to significantly given play to the cured article that obtained by the present invention painted less, resistance to cracking and the excellent such effect of the transparency, the compound of preferred polybasic acid anhydride represented by above-mentioned general formula (1).
As such compound, such as, can enumerate: hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene hexahydrophthalic anhydride etc.More than two kinds also can be share by they.
With regard to the usage quantity of polybasic acid anhydride, the mode being preferably 0.8 ~ 1 equivalent according to anhydride group for epoxy group(ing) 1 equivalent in epoxy resin coordinates, and more preferably coordinates according to the mode for 0.9 ~ 1 equivalent.If anhydride group is more than 0.8 equivalent, then solidification becomes abundant, does not worry that the mechanical characteristics of cured article can significantly reduce.In addition, when anhydride group is below 1 equivalent, also similarly can avoid the reduction of the mechanical characteristics of cured article.
With regard to the dendrimer used in the present invention, hydroxyl value is below 550mgKOH/g, and preferred hydroxyl value is 400 ~ 500mgKOH/g.As long as be below 550mgKOH/g, so can prevent from becoming high viscosity.
In addition, consider from problems such as the reductions of high viscosity, transparency, preferable weight-average molecular weight is less than 2000, is more preferably 1000 ~ 2000.
Preferably use the dendrimer that its viscosity is 10Pas (25 DEG C) further, be more preferably 1 ~ 10Pas (25 DEG C).
The resin combination obtained according to the present invention is low viscosity and process is easy, and the feature of the cured article obtained be painted less, resistance to cracking equal strength and the transparency excellent, in order to play above-mentioned effect more significantly, preferred dendrimer is polyester.In addition, more preferably: on the core with at least 1 reactive epoxy group(ing) or hydroxyl, addition has the polyester that at least 1 branching number of times (from generation to generation) is 1 ~ 50, preferred branched number of times is the dihydroxy monocarboxylate of 1 ~ 10.
As preferred core, list: the alcohols such as neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, 2-butyl-2-ethyl-1,3-propane diol, the epoxides etc. such as the glycidyl ester of monocarboxylic acid, the glycidyl ether of monohydroxy-alcohol.
As dihydroxy monocarboxylate, list: two (hydroxymethyl) propionic acid of 2,2-, 2,2-two (hydroxymethyl) butyric acid etc.There is no particular restriction for the manufacture method of the dendrimer used in the present invention, can apply known method.
In the present invention, with regard to dendrimer, relative to polybasic acid anhydride 100 weight part, preferably comprise 1 ~ 60 weight part, more preferably comprise 10 ~ 50 weight parts.As long as the content of dendrimer is more than 1 weight part, the obdurability of so obtained cured article is abundant, does not worry that resistance to cracking reduces.In addition, as long as the content of dendrimer is below 60 weight parts, so can not becomes high viscosity and easily process, also not worrying that the second-order transition temperature of obtained cured article can reduce significantly, in practical preferably.
The epoxy resin used in the present invention is not particularly limited, but from the viewpoint of photostabilization and thermotolerance, be preferably alicyclic epoxy resin.Alicyclic epoxy resin is, there is the resin of the epoxy group(ing) of alicyclic skeleton and more than 2 in 1 molecule, such as, list: 3 ', 4 '-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate, two (3,4-epoxycyclohexyl-methyl) adipic acid ester, vinyl cyclohexene dioxide, Hydrogenated Bisphenol A diglycidylether etc.More than two kinds also can be share by they.
In addition, the epoxy resin beyond alicyclic epoxy resin can also be used according to object.As such epoxy resin, such as, list: by the reaction of the bisphenols such as dihydroxyphenyl propane, bisphenol S and epoxy chloropropane and the bisphenol-type epoxy resin obtained, by the reaction of phenol novolacs and epoxy chloropropane and the phenol novolak type epoxy resin obtained, by the reaction of polycarboxylic acid and epoxy chloropropane and the glycidyl ester type epoxy resin etc. obtained.More than two kinds also can be share by they.
For the usage quantity of the epoxy resin beyond these alicyclic epoxy resins, relative to alicyclic epoxy resin 100 weight part, be preferably 0 ~ 80 weight part, be more preferably 0 ~ 20 weight part.As long as the usage quantity of the epoxy resin beyond alicyclic epoxy resin is below 80 weight parts, so can prevent the photostabilization of cured article and thermotolerance from reducing.
In the present invention, by the epoxy curing agent by polybasic acid anhydride and dendrimer mixing thus acquisition target, there is no particular restriction for its manufacture method, can apply known method.Further, by this epoxy curing agent and epoxy resin being mixed thus obtaining composition epoxy resin, there is no particular restriction for its manufacture method, can apply known method.In addition, also by dendrimer and polybasic acid anhydride are separately mixed with epoxy resin thus obtain composition epoxy resin.
With regard to the composition epoxy resin in the present invention, curing catalyst can be added aptly according to object.As curing catalyst, such as, list: the imidazoles such as 2-ethyl-4-methylimidazole, 1-Methylimidazole, the tertiary amines such as benzyl dimethyl amine, DMA, the quaternary ammonium salt such as tetramethyl ammonium chloride, benzyltriethylammoinium chloride, Si Zheng Ding Ji Phosphonium o, the phosphonium salts such as the even phosphorus dithionate of o-diethyl, 4-butyl-phosphonium benzotriazole Yan, the metal-salt such as zinc octoate, Zinic stearas, the metal complexes etc. such as zinc acetylacetonate, benzoyl acetone zinc.
About the use level in the composition epoxy resin when using curing catalyst, being preferably 0.01 ~ 8 % by weight, being more preferably 0.1 ~ 5 % by weight.If the use level of curing catalyst is more than 0.01 % by weight, so sufficient effect can be obtained.In addition, if the use level of curing catalyst is less than 8 % by weight, the situation that the painted or thermotolerance of obtained cured article reduces so can be alleviated.
In composition epoxy resin of the present invention, in the scope of characteristic of not losing obtained cured article, various additive can be added further according to object.As additive, list: toughner (flexibilizer), thermo-stabilizer, UV light absorber, fire retardant, static inhibitor, defoamer, thixotropy conferring agents, releasing agent etc.Further, such as list: for the antioxidant of the photostabilization and thermotolerance that improve cured article further, for controlling the chain-transfer agent of the polyreaction in solidification, for improveing the weighting agent of the mechanical properties of cured article, cementability, treatability, softening agent, stress relieving agent (low ying power drug), coupling agent, dyestuff, light scattering agent etc.
By the composition epoxy resin be heating and curing in the present invention, thus can obtain painted less, the cured article of resistance to cracking and transparency excellence.There is no particular restriction for the manufacture method of cured article, can apply known method.There is no particular restriction for the temperature and time be heating and curing, and is preferably 90 ~ 180 DEG C, 1 ~ 12 hour.By coating, embedding (potting), impregnating method, composition epoxy resin is arranged on the surface of LED luminous element etc., by being heating and curing, thus can sealing LED luminous element etc.
Optical semiconductor device of the present invention is by the device of the optical semiconductors such as above-mentioned cured article sealing LED luminous element, photodiode cell, be painted less, resistance to cracking and the transparency be excellent, and then photostabilization and the also excellent device of thermotolerance.
Embodiment
Below, by embodiment, more specific description is carried out to the present invention.The present invention is not limited to these embodiments.
(embodiment 1)
Relative to polyester dendrimers shape polymer (hydroxyl value 470mgKOH/g, weight-average molecular weight 1800, viscosity 7.6Pas (25 DEG C), BOLTORN P-1000: Bai Situo company (Perstorp society) trade(brand)name processed) 20 weight parts, add 4-methylhexahydrophthalic anhydride (HN-7000: Hitachi Chemical Co., Ltd.'s system/anhydride equivalent 168 (g/eq)) 116 weight parts as polybasic acid anhydride, be heated to 70 DEG C and stir, dissolve until become evenly, thus obtain epoxy curing agent (I).
For epoxy curing agent (I) 136 weight part, add 3 ' as epoxy resin, 4 '-epoxycyclohexyl-methyl-3, 4-epoxycyclohexane carboxylate (CELLOXIDE 2021P:DAICEL chemical industry Co., Ltd. (DAICEL CHEMICAL INDUSTRIES, LTD.) trade(brand)name/epoxy equivalent (weight) 138 (g/eq) processed) 100 weight parts, as the Si Zheng Ding Ji Phosphonium o of curing catalyst, even phosphorus dithionate (Hishikorin (ヒ シ コ ー リ Application) PX-4ET: Nippon Chemical Ind's trade(brand)name) 1 weight part of o-diethyl, as 9 of stablizer, 10-dihydro-9-phospha-10-oxa-phenanthrene-9-oxide compound (HCA: three photochemistry Co., Ltd. systems) 1 weight part, be heated to 80 DEG C and stir, dissolve until become even thus obtain composition epoxy resin (I).
Then, under reduced pressure by after composition epoxy resin (I) fully froth breaking, a part being flow into lightly (a) is placed with in the metal plate (schale) of metal clip in central authorities, remaining part flows in the mould of (b) tabular, respectively 120 DEG C heating 1 hour after further 150 DEG C heating 4 hours, thus acquisition two kinds of cured articles (I).
(embodiment 2)
Except carry out the polyester dendrimers shape polymer of alternative 20 weight parts with the polyester dendrimers shape polymer of 40 weight parts except, operate similarly to Example 1, thus obtain epoxy curing agent (II).
Except using epoxy curing agent (II) 156 weight part to come, except alternative epoxy curing agent (I), to operate similarly to Example 1, thus obtain composition epoxy resin (II).Further, operate similarly to Example 1, thus obtain cured article (II).
(embodiment 3)
Except using the mixture of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride (hereinafter referred to as 3 & 4-methylhexahydrophthalic anhydrides.HN-5500E: Hitachi Chemical Co., Ltd.'s system/anhydride equivalent 168 (g/eq)) 116 weight parts as beyond polybasic acid anhydride, operate similarly to Example 1, thus obtain epoxy curing agent (III).
By epoxy curing agent (III), operate similarly to Example 1, thus obtain composition epoxy resin (III).Further, operate similarly to Example 1, thus obtain cured article (III).
(embodiment 4)
Except carry out the polyester dendrimers shape polymer of alternative 20 weight parts with the polyester dendrimers shape polymer of 40 weight parts except, operate similarly to Example 3, thus obtain epoxy curing agent (IV).
Except using epoxy curing agent (IV) 156 weight part to come, except alternative epoxy curing agent (I), to operate similarly to Example 1, thus obtain composition epoxy resin (IV).Further, operate similarly to Example 1, thus obtain cured article (IV).
(comparative example 1)
Except using polyester dendrimers shape polymer (the hydroxyl value 600mgKOH/g of 20 weight parts, weight-average molecular weight 1800, viscosity 32.8Pas (25 DEG C), BOLTORN P-500: Bai Situo Inc. trade(brand)name) as beyond dendrimer, operate similarly to Example 1, thus obtain epoxy curing agent (V).
By epoxy curing agent (V), operate similarly to Example 1, thus obtain composition epoxy resin (V).Further, operate similarly to Example 1, thus obtain cured article (V).
(comparative example 2)
Except carry out the polyester dendrimers shape polymer of alternative 20 weight parts with the polyester dendrimers shape polymer of 40 weight parts except, operate in the same manner as comparative example 1, thus obtain epoxy curing agent (VI).
Except using epoxy curing agent (VI) 156 weight part to come, except alternative epoxy curing agent (I), to operate similarly to Example 1, thus obtain composition epoxy resin (VI).Further, operate similarly to Example 1, thus obtain cured article (VI).
(comparative example 3)
Do not use polyester dendrimers shape polymer, carry out alternative epoxy curing agent (I) with 4-methylhexahydrophthalic anhydride 116 weight part, in addition, operate similarly to Example 1, thus obtain composition epoxy resin (VII).
By composition epoxy resin (VII), operate similarly to Example 1, thus obtain cured article (VII).
The outward appearance of the tone of composition epoxy resin (I) ~ (VII) obtained in embodiment 1 ~ 4 and comparative example 1 ~ 3 and viscosity, cured article (I) ~ (VII), crack, second-order transition temperature, flexural strength and bending elastic modulus are evaluated, the results are shown in table 1,2.Use (a) in each cured article in fracture evaluation, in the evaluation of other cured article, employ (b).The method of the evaluating characteristics in table 1,2 is as follows.
Tone: compared by range estimation and APHA reference liquid.
Viscosity: at 25 DEG C, with E type viscometer determining.
Outward appearance: judge cured article (b) by range estimation.
Crack: be after the cured article (a) of 2 is placed 20 hours at-30 DEG C by sample number, place 10 hours in room temperature (25 DEG C), confirming have leakless to produce by estimating.
Zero: leakless
×: the crack having a more than place in sample
Second-order transition temperature: the sample cutting out 2mm × 5mm × 5mm from cured article (b), is measured by thermomechanical analyzer (TMA).
Determinator SSC-5200 (Seiko Instruments Inc (Seiko Instruments Inc.) system)
Condition determination load 20g/ per minute heats 10 DEG C
Flexural strength: measure according to the specification designation K7171 of JIS (JIS).
Bending elastic modulus: measure according to above-mentioned JIS K7171.
[table 1]
[table 2]
As shown in table 1,2, judge: the resin combination obtained in embodiment 1 ~ 4 has taken into account low viscosity and flexural strength, and in addition, cured article does not have crack yet, is water white.On the other hand, comparative example 1 due to the use level of dendrimer few, although therefore have the low viscosity compared, flexural strength is poor.With regard to comparative example 2, although flexural strength increases with the use level increase of dendrimer, viscosity becomes very high, and then cured article has been coloured to yellow.In the cured article of comparative example 3, except creating crack, flexural strength is also low, and cured article has been coloured to yellow.
According to the present invention, can low viscosity be obtained and process is easy to composition epoxy resin, and intensity high and painted less, the cured article of resistance to cracking and transparency excellence.
Industry utilizes possibility
According to the present invention, can obtain the epoxy curing agent forming following composition epoxy resin, described composition epoxy resin is low viscosity after blending and process is easy, and the intensity of cured article is good; Thus, can obtain painted less, the cured article of resistance to cracking and transparency excellence.
Claims (14)
1. an epoxy curing agent, is characterized in that, comprises the dendrimer of polybasic acid anhydride and hydroxyl value 400 ~ 500mgKOH/g,
Described polybasic acid anhydride is the mixture of 4-methylhexahydrophthalic anhydride or 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride.
2. epoxy curing agent according to claim 1, is characterized in that, the weight-average molecular weight of described dendrimer is less than 2000.
3. epoxy curing agent according to claim 1 and 2, is characterized in that, the viscosity of described dendrimer at 25 DEG C is below 10Pas.
4. epoxy curing agent according to claim 1 and 2, is characterized in that, described dendrimer is polyester.
5. epoxy curing agent according to claim 1 and 2, is characterized in that, relative to described polybasic acid anhydride 100 weight part, comprises the described dendrimer of 1 ~ 60 weight part.
6. a composition epoxy resin, is characterized in that, comprises the dendrimer of epoxy resin, polybasic acid anhydride and hydroxyl value 400 ~ 500mgKOH/g,
Described polybasic acid anhydride is the mixture of 4-methylhexahydrophthalic anhydride or 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride.
7. composition epoxy resin according to claim 6, is characterized in that, the weight-average molecular weight of described dendrimer is less than 2000.
8. the composition epoxy resin according to claim 6 or 7, is characterized in that, the viscosity of described dendrimer at 25 DEG C is below 10Pas.
9. the composition epoxy resin according to claim 6 or 7, is characterized in that, described dendrimer is polyester.
10. the composition epoxy resin according to claim 6 or 7, is characterized in that, relative to described polybasic acid anhydride 100 weight part, comprises the described dendrimer of 1 ~ 60 weight part.
11. composition epoxy resins according to claim 6 or 7, it is characterized in that, described epoxy resin is included in 1 molecule the alicyclic epoxy resin of the epoxy group(ing) with alicyclic skeleton and more than 2.
12. composition epoxy resins according to claim 11, it is characterized in that, described alicyclic epoxy resin is selected from 3 ', 4 '-epoxycyclohexyl-methyl-3, at least one resin in 4-epoxycyclohexane carboxylate, two (3,4-epoxycyclohexyl-methyl) adipic acid ester, vinyl cyclohexene dioxide, Hydrogenated Bisphenol A diglycidylether.
13. 1 kinds of cured articles, is characterized in that, form by making the composition epoxy resin described in any one in claim 6 ~ 12 be cured.
14. 1 kinds of optical semiconductor devices, is characterized in that, by forming with cured article sealing optical semiconductor according to claim 13.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008-194808 | 2008-07-29 | ||
| JP2008194808 | 2008-07-29 | ||
| JP2009127596 | 2009-05-27 | ||
| JP2009-127596 | 2009-05-27 | ||
| CN2009801299408A CN102112516A (en) | 2008-07-29 | 2009-07-23 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801299408A Division CN102112516A (en) | 2008-07-29 | 2009-07-23 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104693419A true CN104693419A (en) | 2015-06-10 |
| CN104693419B CN104693419B (en) | 2017-11-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201510131992.6A Active CN104693419B (en) | 2008-07-29 | 2009-07-23 | Epoxy curing agent, composition epoxy resin, its solidfied material and optical semiconductor device |
| CN2009801299408A Pending CN102112516A (en) | 2008-07-29 | 2009-07-23 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
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| CN2009801299408A Pending CN102112516A (en) | 2008-07-29 | 2009-07-23 | Epoxy resin curing agent, epoxy resin composition, hardened material thereof, and optical semiconductor device |
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| JP (1) | JP5522043B2 (en) |
| KR (1) | KR101636587B1 (en) |
| CN (2) | CN104693419B (en) |
| TW (1) | TWI464192B (en) |
| WO (1) | WO2010013638A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433023A (en) * | 2015-08-13 | 2017-02-22 | 中国石油化工股份有限公司 | Method for preparing elastic epoxy resin for epoxy resin casting dry type transformer |
| CN111303384A (en) * | 2020-03-26 | 2020-06-19 | 上海稳优实业有限公司 | Temperature latent curing agent and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI380916B (en) * | 2010-03-17 | 2013-01-01 | Taiyen Biotech Co Ltd | Composition of salt-based sculptured substrate and method of manufacturing thereof |
| CN102971355B (en) * | 2010-06-30 | 2015-07-08 | 日本化药株式会社 | Polyvalent carboxylic acid composition, curing agent composition, and curable resin composition containing polyvalent carboxylic acid composition or curing agent composition as curing agent for epoxy resin |
| US10886506B2 (en) * | 2015-03-30 | 2021-01-05 | Dai Nippon Printing Co., Ltd. | Cell packaging material, method for manufacturing same, and cell |
| CN112375340B (en) * | 2021-01-15 | 2021-03-26 | 武汉市三选科技有限公司 | Circuit laminated film for wafer level packaging sealing, and preparation method and application thereof |
| US11286386B1 (en) | 2021-01-15 | 2022-03-29 | Wuhan Choice Technology Co., Ltd. | Circuit build-up film for wafer-level packaging, and fabrication method and use thereof |
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| WO2002066541A1 (en) * | 2001-02-16 | 2002-08-29 | Perstorp Specialty Chemicals Ab | Process for manufacture of a carboxy terminated dendritic polyester |
| JP2007314740A (en) * | 2006-04-26 | 2007-12-06 | Hitachi Chem Co Ltd | Epoxy resin composition, its cured product and photosemiconductor device |
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| GB9913627D0 (en) * | 1999-06-12 | 1999-08-11 | Ciba Geigy Ag | Process for the preparation of reaction products of cycloaliphatic epoxides with multifunctional hydroxy compounds |
| US20060252892A1 (en) * | 2005-05-03 | 2006-11-09 | Basheer Rafil A | Hyperbranched polymer and cycloaliphatic epoxy resin thermosets |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002066541A1 (en) * | 2001-02-16 | 2002-08-29 | Perstorp Specialty Chemicals Ab | Process for manufacture of a carboxy terminated dendritic polyester |
| JP2007314740A (en) * | 2006-04-26 | 2007-12-06 | Hitachi Chem Co Ltd | Epoxy resin composition, its cured product and photosemiconductor device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106433023A (en) * | 2015-08-13 | 2017-02-22 | 中国石油化工股份有限公司 | Method for preparing elastic epoxy resin for epoxy resin casting dry type transformer |
| CN106433023B (en) * | 2015-08-13 | 2018-09-21 | 中国石油化工股份有限公司 | The method for preparing Cast Resin Dry-Type Transformer elastic epoxy resin |
| CN111303384A (en) * | 2020-03-26 | 2020-06-19 | 上海稳优实业有限公司 | Temperature latent curing agent and preparation method thereof |
| CN111303384B (en) * | 2020-03-26 | 2022-08-19 | 上海稳优实业有限公司 | Temperature latent curing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI464192B (en) | 2014-12-11 |
| KR101636587B1 (en) | 2016-07-05 |
| CN104693419B (en) | 2017-11-24 |
| CN102112516A (en) | 2011-06-29 |
| JPWO2010013638A1 (en) | 2012-01-12 |
| WO2010013638A1 (en) | 2010-02-04 |
| TW201008970A (en) | 2010-03-01 |
| JP5522043B2 (en) | 2014-06-18 |
| KR20110055481A (en) | 2011-05-25 |
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