CN104693419B - Epoxy curing agent, composition epoxy resin, its solidfied material and optical semiconductor device - Google Patents
Epoxy curing agent, composition epoxy resin, its solidfied material and optical semiconductor device Download PDFInfo
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- CN104693419B CN104693419B CN201510131992.6A CN201510131992A CN104693419B CN 104693419 B CN104693419 B CN 104693419B CN 201510131992 A CN201510131992 A CN 201510131992A CN 104693419 B CN104693419 B CN 104693419B
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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 present invention relates to epoxy curing agent, composition epoxy resin, its solidfied material and optical semiconductor device.The present invention provides a kind of epoxy curing agent, it is characterized in that, 400~500mgKOH/g of polybasic acid anhydride and hydroxyl value dendrimer is included, the polybasic acid anhydride is 4 methylhexahydrophthalic anhydrides or the mixture of 3 methylhexahydrophthalic anhydrides and 4 methylhexahydrophthalic anhydrides.
Description
The present invention is
On July 23rd, 2009, entitled " epoxy curing agent, composition epoxy resin, its solidfied material and photosemiconductor dress
Put " patent application divisional application.
Technical field
The present invention relates to epoxy curing agent, composition epoxy resin, its solidfied material and optical semiconductor device.Enter one
Step specifically, be related to for formed coloring less, epoxy curing agent, the ring of resistance to cracking and the excellent solidfied material of the transparency
Epoxy resin composition, its solidfied material and optical semiconductor device.
Background technology
Generally, the epoxy resin cured product obtained by acid anhydrides and epoxy resin, the cheap and transparency, electric insulating quality,
Chemical proofing, moisture-proof, cementability etc. are excellent, for insulating material, semi-conducting material, adhesives, coating material
The various uses such as material.As one it is representational use example, can enumerate for protecting light emitting diode (Light-emitting
diode：Hereinafter referred to as LED) light-emitting component material for sealing.In recent years, with the light source and fluorescence of short-wavelength light will be sent
The popularization for the White LED that body is combined, encapsulate the deterioration expected admittedly and have been considered as problem.
I.e., in the case of white leds, due to the light source using higher energy, therefore compared to existing red, green
LED for, produce material for sealing deterioration and easily colour, the problem of LED lifetime is such.In addition, with by lighting
Miniaturization and the propulsion of high current, the caused heat in the case of by LED long-term lightings caused by the improvement of element
Also become big, thus can similarly cause the deterioration of encapsulating material.
In the further popularization of epoxy resin, this deterioration caused by light, heat is carried out suppressing to turn into important
Problem.As the method for solving the problem, it is thus proposed that using alicyclic epoxy resin come substitute easily because light, heat and it is bad
The composition epoxy resin of the aromatic epoxy resin of change (for example, referring to patent document 1,2 and 3).
On the other hand, for having used the composition epoxy resin of this alicyclic epoxy resin, there are as follows
Shortcoming, i.e. the solidfied material obtained lacks obdurability, and crack is easily produced because the conditions such as temperature change.Asked to solve this
Topic, as make by composition epoxy resin obtain solidfied material become tough method, it is known to use includes various macromolecules
Modifying agent technology.It has been proposed, for example, that：By adding polyester resin in composition epoxy resin, so as to not damage
In the case of the transparency of evil solidfied material, improve the method for obdurability (for example, referring to patent document 4).
But usual polyester resin easily carries color when condensation, therefore in the hair described in above-mentioned patent document 4
In bright, as shown in embodiment, solidfied material significantly colours yellowly to brown.Therefore, for example such as above-mentioned LED material for sealing
In terms of requiring the purposes for water white transparency like that, problem in practical use be present.
It is in order to solve the problems, such as such, it is thus proposed that the technology of addition dendrimer is (for example, referring to patent document
5)。
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-196151 publications
Patent document 2：Japanese Unexamined Patent Publication 2003-012896 publications
Patent document 3：Japanese Unexamined Patent Publication 2003-221490 publications
Patent document 4：Japanese Unexamined Patent Publication 2004-131553 publications
Patent document 5：Japanese Unexamined Patent Publication 2007-314740 publications
The content of the invention
The invention problem to be solved
But for the technology of foregoing addition dendrimer, tendency is uprised because mixed viscosity is present,
And the intensity of solidfied material has deterioration, therefore reluctant problem be present.Thus, will particularly in LED sealing
It is unsuitable in the case of asking trickle processing, surface smoothness.
The present invention develops in view of the above problems, and it provides a kind of strong after taking into account mixed low viscosity and solidifying
Degree and can be formed coloring less, the epoxy curing agent of resistance to cracking and the excellent solidfied material of the transparency.In addition, the present invention carries
For low-viscosity epoxy resin combination, coloring less, resistance to cracking and the excellent epoxy resin composition thing of the transparency with
And optical semiconductor device.
Solves the technical scheme of problem
The present inventor, had made intensive studies to solve above-mentioned problem, the following fact is as a result found, so as to complete
The present invention：Into polybasic acid anhydride addition be mixed with the high molecular epoxy curing agent of specific dendroid as modifying agent
In the presence of, low viscosity and the easy composition epoxy resin of processing are readily available, it is intensity, resistance in addition, it is few to be readily available coloring
Cracking behavior and transparent excellent solidfied material.
The present invention relates to following [1]~[15].
[1] a kind of epoxy curing agent, the dendroid high score comprising polybasic acid anhydride and below hydroxyl value 550mgKOH/g
Son.
[2] epoxy curing agent recorded according to [1], wherein, the weight average molecular weight of dendrimer for 2000 with
Under.
[3] epoxy curing agent recorded according to [1] or [2], wherein, viscosity of the dendrimer at 25 DEG C is
Below 10Pas.
[4] epoxy curing agent recorded according to any one of [1]~[3], wherein, polybasic acid anhydride is following logical
Compound represented by formula (1).
[chemical formula 1]
(in formula, R1~R4Hydrogen atom, or the alkyl of the carbon number 1~4 of straight or branched are represented independently of one another,
Wherein, selected from R1~R4In the two also can with reference to and form ring.)
[5] epoxy curing agent recorded according to any one of [1]~[4], wherein, dendrimer is poly-
Ester.
[6] epoxy curing agent recorded according to any one of [1]~[5], wherein, relative to polybasic acid anhydride
100 parts by weight, include the parts by weight of dendrimer 1~60.
[7] a kind of composition epoxy resin, the asphalt mixtures modified by epoxy resin recorded comprising any one of epoxy resin and [1]~[6]
Fat curing agent.
[8] a kind of composition epoxy resin, epoxy resin, polybasic acid anhydride and below hydroxyl value 550mgKOH/g tree are included
Dendritic macromolecule.
[9] composition epoxy resin recorded according to [8], wherein, the weight average molecular weight of dendrimer for 2000 with
Under.
[10] composition epoxy resin recorded according to [8] or [9], wherein, viscosity of the dendrimer at 25 DEG C
For below 10Pas.
[11] composition epoxy resin recorded according to any one of [8]~[10], wherein, polybasic acid anhydride is following
Compound represented by formula (1).
[chemical formula 2]
(in formula, R1~R4Hydrogen atom, or the alkyl of the carbon number 1~4 of straight or branched are represented independently of one another,
Wherein, selected from R1~R4In the two also can with reference to and form ring.)
[12] composition epoxy resin recorded according to any one of [8]~[11], wherein, dendrimer is poly-
Ester.
[13] composition epoxy resin recorded according to any one of [8]~[12], wherein, relative to polybasic acid anhydride
100 parts by weight, include the parts by weight of dendrimer 1~60.
[14] a kind of solidfied material, formed by the epoxy resin composition for recording any one of [7]~[13].
[15] a kind of optical semiconductor device, the solidfied material recorded by using [14] form optical semiconductor sealing.
For present invention, and in Japanese Patent Application 2008-194808, Yi Ji filed in 29 days July in 2008
Theme described in Japanese Patent Application filed in 27 days Mays in 2009 2009-127596 is associated, and disclosures of which is to draw
Quoted with mode in herein.
Invention effect
According to the present invention, the epoxy curing agent to form following composition epoxy resin, the epoxy resin can be obtained
Composition after blending for low viscosity and processing it is easy, and the intensity of solidfied material is good, thus, can obtain coloring less, resistance to open
Fragility and transparent excellent solidfied material.
Embodiment
Hereinafter, the present invention is described in detail.
There is no particular restriction for the polybasic acid anhydride used in the present invention, for example, can enumerate：Succinic anhydride, maleic anhydride, neighbour
Phthalate anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylendomethylene tetrahydrophthalic acid
Acid anhydride, itaconic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic anhydride etc..They can also share more than two kinds.
In order to significantly given play to the coloring of solidfied material obtained by the present invention less, resistance to cracking and the transparency it is excellent so
Effect, preferably polybasic acid anhydride be above-mentioned formula (1) represented by compound.
As such compound, for example, can enumerate：Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, first
Base endo-methylene group hexahydrophthalic anhydride etc..They can also share more than two kinds.
For the usage amount of polybasic acid anhydride, preferably according to sour for the equivalent of epoxy radicals 1 in epoxy resin
Anhydride group coordinates for the mode of 0.8~1 equivalent, more preferably coordinates in the way of for 0.9~1 equivalent.If anhydride group is
More than 0.8 equivalent, then solidification becomes abundant, without worrying that the mechanical property of solidfied material can significantly reduce.In addition, it is in anhydride group
In the case of below 1 equivalent, the reduction of the mechanical property of solidfied material also can be similarly avoided.
For the dendrimer used in the present invention, hydroxyl value is below 550mgKOH/g, preferably hydroxyl value be 400~
500mgKOH/g.As long as it is below 550mgKOH/g, then can prevent from being changed into high viscosity.
In addition, from high viscosity, transparency reduction the problems such as consider, preferable weight-average molecular weight be less than 2000, more preferably
For 1000~2000.
Further preferably using the dendrimer that its viscosity is 10Pas (25 DEG C), more preferably 1~10Pas
(25℃)。
The resin combination obtained according to the present invention is low viscosity and handles easily, and the spy of the solidfied material obtained
Sign be colour less, resistance to cracking equal strength and the transparency it is excellent, in order to significantly more play the effect above, preferably dendroid
Macromolecule is polyester.In addition, more preferably：On the core with least one reactivity epoxy radicals or hydroxyl, addition has at least one
Branched number (generation) is the polyester for the dihydroxy monocarboxylate that 1~50, preferred branched number is 1~10.
As preferable core, include：Neopentyl glycol, trimethylolpropane, pentaerythrite, 2- butyl -2- ethyls -1,3-
Epoxides such as the alcohols such as propane diol, the ethylene oxidic ester of monocarboxylic acid, the glycidol ether of monohydric alcohol etc..
As dihydroxy monocarboxylate, include：Double (hydroxymethyl) propionic acid of 2,2-, double (hydroxymethyl) butyric acid of 2,2- 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, for dendrimer, relative to the parts by weight of polybasic acid anhydride 100,1~60 is preferably comprised
Parts by weight, more preferably comprising 10~50 parts by weight.As long as the content of dendrimer is more than 1 parts by weight, then is obtained
Solidfied material obdurability it is abundant, without worry resistance to cracking reduce.In addition, as long as the content of dendrimer is 60 weight
Below part, then high viscosity will not be changed into and be easily processed, without the glass transition temperature for worrying obtained solidfied material
Degree can significantly decrease, in practical preferably.
The epoxy resin used in the present invention is not particularly limited, but from the aspect of light resistance and heat resistance, it is excellent
Elect alicyclic epoxy resin as.Alicyclic epoxy resin is to have alicyclic skeleton and the epoxy radicals of more than 2 in 1 molecule
Resin, for example, including：3 ', 4 '-epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylates, double (3,4- epoxy hexamethylenes
Ylmethyl) hexanedioic acid ester, vinyl cyclohexene dioxide, hydrogenated bisphenol A diglycidyl ether etc..They also can by two kinds with
On share.
In addition, the epoxy resin beyond alicyclic epoxy resin can also be used according to purpose.As such asphalt mixtures modified by epoxy resin
Fat, for example, including：By the reaction of the bisphenols such as bisphenol-A, bisphenol S and epoxychloropropane and the biphenol type epoxy tree that obtains
Fat, by the reaction of phenol novolacs and epoxychloropropane and the phenol novolak type epoxy resin that obtains, by polynary
The reaction of carboxylic acid and epoxychloropropane and glycidyl ester type epoxy resin for obtaining etc..They can also share more than two kinds.
For the usage amount of the epoxy resin beyond these alicyclic epoxy resins, relative to alicyclic epoxy resin
100 parts by weight, preferably 0~80 parts by weight, more preferably 0~20 parts by weight.As long as the epoxy beyond alicyclic epoxy resin
The usage amount of resin is below 80 parts by weight, then the light resistance and heat resistance that can prevent solidfied material reduce.
In the present invention, can be by the way that polybasic acid anhydride and dendrimer be mixed so as to obtain the epoxy resin of target
Curing agent, there is no particular restriction for its manufacture method, can apply known method.Further, can be by by the epoxy curing agent
Mixed with epoxy resin so as to obtain composition epoxy resin, there is no particular restriction for its manufacture method, can apply known method.Separately
Outside, also can be by the way that dendrimer and polybasic acid anhydride be separately mixed with epoxy resin so as to obtain epoxy resin
Composition.
For the composition epoxy resin in the present invention, curing accelerator can suitably be added according to purpose.As
Curing accelerator, for example, including：The imidazoles such as 2-ethyl-4-methylimidazole, 1- methylimidazoles, benzyldimethylamine, 2,4, N, N-
The quaternary ammonium salt such as the tertiary amines such as dimethylaniline, tetramethyl ammonium chloride, benzyltriethylammoinium chloride, Si Zheng Ding Ji Phosphonium o, o- diethyl are even
Phosphorus dithionate, the metal salt such as 4-butyl-phosphonium BTA Yan Deng phosphonium salts, zinc octoate, zinc stearate, zinc acetylacetonate, benzene first
Metal complexes such as acyl acetone zinc etc..
On the use level in using the composition epoxy resin in the case of curing accelerator, preferably 0.01~8
Weight %, more preferably 0.1~5 weight %.If the use level of curing accelerator is more than 0.01 weight %, then can be obtained
Sufficient effect.In addition, if the use level of curing accelerator is below 8 weight %, then can mitigate obtained solidfied material
The situation that coloring or heat resistance reduce.
, can root in the range of the characteristic of obtained solidfied material is not lost in the composition epoxy resin of the present invention
Various additives are further added according to purpose.As additive, include：Toughener (flexibilizer), heat stabilizer,
Ultra-violet absorber, fire retardant, antistatic additive, defoamer, thixotropy conferring agents, releasing agent etc..Further, such as include：
For further improving the light resistance of solidfied material and the antioxidant of heat resistance, for controlling the chain of the polymerisation in solidifying to turn
Move agent, for improve the mechanical properties of solidfied material, cementability, treatability filler, plasticizer, stress elimination agent (low ying power
Change drug), coupling agent, dyestuff, light scattering agent etc..
By the composition epoxy resin being heating and curing in the present invention, so as to obtain coloring less, resistance to cracking and transparent
The excellent solidfied material of property.There is no particular restriction for the manufacture method of solidfied material, can apply known method.The temperature that is heating and curing and when
Between there is no particular restriction, preferably 90~180 DEG C, 1~12 hour.The methods of by coating, embedding (potting), dipping, will
Composition epoxy resin is arranged on the surface of LED light-emitting component etc., by being heating and curing, so as to sealing LED light-emitting component
Deng.
The optical semiconductor device of the present invention is by light such as above-mentioned solidfied material sealing LED light-emitting component, photodiode cells
The device that semiconductor element forms, be colour less, resistance to cracking and the transparency it is excellent, and then light resistance and heat resistance are also excellent
Device.
Embodiment
Hereinafter, more specific description is carried out to the present invention by embodiment.The present invention is not only restricted to these embodiments.
(embodiment 1)
Relative to polyester dendrimers shape macromolecule (hydroxyl value 470mgKOH/g, weight average molecular weight 1800, viscosity 7.6Pas (25
DEG C), BOLTORN P-1000：Bai Situo companies (Perstorp societies) trade name processed) for 20 parts by weight, add and be used as polynary carboxylic
4- methylhexahydrophthalic anhydrides (the HN-7000 of acid anhydrides：The Hitachi Chemical Co., Ltd.'s system/(g/ of anhydride equivalent 168
Eq)) 116 parts by weight, 70 DEG C is heated to and is stirred, dissolving is until be changed into uniform, so as to obtain epoxy curing agent (I).
For the parts by weight of epoxy curing agent (I) 136,3 ', 4 '-epoxy hexamethylene as epoxy resin is added
Ylmethyl -3,4- epoxycyclohexane carboxylates (CELLOXIDE 2021P：DAICEL chemical industry Co., Ltd. (DAICEL
CHEMICAL INDUSTRIES, LTD.) trade name/epoxide equivalent 138 (g/eq) processed) 100 parts by weight, as curing accelerator
Si Zheng Ding Ji Phosphonium o, o- diethyl idol phosphorus dithionate (Hishikorin (ヒ シ コ ー リ Application) PX-4ET：The chemical work of Japan
Industry Co. Ltd. system trade name) 1 parts by weight, the 9,10- dihydro -9- phospha -10- oxa- phenanthrene -9- oxides as stabilizer
(HCA：Three photochemistry Co. Ltd. systems) 1 parts by weight, it is heated to 80 DEG C and stirs, dissolving is until be changed into uniformly so as to obtain epoxy
Resin combination (I).
Then, after composition epoxy resin (I) is fully defoamed under reduced pressure, a part is lightly flow into
(a) it is placed with center in the metal plate (schale) of metal clip, remaining part flows into the mould of (b) tabular
In, further heated 4 hours at 150 DEG C afterwards within 1 hour in 120 DEG C of heating respectively, so as to obtain two kinds of solidfied materials (I).
(embodiment 2)
In addition to polyester dendrimers shape macromolecule of the polyester dendrimers shape macromolecule of 40 parts by weight to substitute 20 parts by weight,
Operate similarly to Example 1, so as to obtain epoxy curing agent (II).
In addition to substituting epoxy curing agent (I) using the parts by weight of epoxy curing agent (II) 156, with implementation
Example 1 similarly operates, so as to obtain composition epoxy resin (II).Further, operate similarly to Example 1, so as to obtain
Solidfied material (II).
(embodiment 3)
Except using the mixture of 3- methylhexahydrophthalic anhydrides and 4- methylhexahydrophthalic anhydrides (below,
Referred to as 3＆4- methylhexahydrophthalic anhydrides.HN-5500E：The Hitachi Chemical Co., Ltd.'s system/(g/ of anhydride equivalent 168
Eq beyond)) 116 parts by weight are as polybasic acid anhydride, operate similarly to Example 1, so as to obtain epoxy curing agent
(III)。
By epoxy curing agent (III), operate similarly to Example 1, so as to obtain composition epoxy resin
(III).Further, operate similarly to Example 1, so as to obtain solidfied material (III).
(embodiment 4)
In addition to polyester dendrimers shape macromolecule of the polyester dendrimers shape macromolecule of 40 parts by weight to substitute 20 parts by weight,
Operate similarly to Example 3, so as to obtain epoxy curing agent (IV).
In addition to substituting epoxy curing agent (I) using the parts by weight of epoxy curing agent (IV) 156, with implementation
Example 1 similarly operates, so as to obtain composition epoxy resin (IV).Further, operate similarly to Example 1, so as to obtain
Solidfied material (IV).
(comparative example 1)
Except polyester dendrimers shape macromolecule (hydroxyl value 600mgKOH/g, weight average molecular weight 1800, the viscosity using 20 parts by weight
32.8Pas (25 DEG C), BOLTORN P-500：Bai Situo company systems trade name) it is used as beyond dendrimer, with implementation
Example 1 similarly operates, so as to obtain epoxy curing agent (V).
By epoxy curing agent (V), operate similarly to Example 1, so as to obtain composition epoxy resin (V).Enter
One step, is operated similarly to Example 1, so as to obtain solidfied material (V).
(comparative example 2)
In addition to polyester dendrimers shape macromolecule of the polyester dendrimers shape macromolecule of 40 parts by weight to substitute 20 parts by weight,
Operated in the same manner as comparative example 1, so as to obtain epoxy curing agent (VI).
In addition to substituting epoxy curing agent (I) using the parts by weight of epoxy curing agent (VI) 156, with implementation
Example 1 similarly operates, so as to obtain composition epoxy resin (VI).Further, operate similarly to Example 1, so as to obtain
Solidfied material (VI).
(comparative example 3)
Without using polyester dendrimers shape macromolecule, asphalt mixtures modified by epoxy resin is substituted with the parts by weight of 4- methylhexahydrophthalic anhydrides 116
Fat curing agent (I), in addition, is operated similarly to Example 1, so as to obtain composition epoxy resin (VII).
By composition epoxy resin (VII), operate similarly to Example 1, so as to obtain solidfied material (VII).
To composition epoxy resin (I)~(VII) tone that is obtained in embodiment 1~4 and comparative example 1~3 and viscous
Degree, solidfied material (I)~(VII) outward appearance, crack, glass transition temperature, bending strength and the modulus of elasticity in static bending are evaluated,
The results are shown in table 1,2.(a) in each solidfied material is used in fracture evaluation, (b) has been used in the evaluation of other solidfied materials.
The method of evaluating characteristics in table 1,2 is as follows.
Tone：By estimating compared with APHA titers.
Viscosity：At 25 DEG C, determined with E types viscosimeter.
Outward appearance：Judge solidfied material (b) by estimating.
Crack：After the solidfied material (a) that sample number is 2 is placed 20 hours at -30 DEG C, put in room temperature (25 DEG C)
Put 10 hours, confirm to have free from flaw generation by estimating.
○：Free from flaw
×：There is the crack more than at one in sample
Glass transition temperature：2mm × 5mm × 5mm sample is cut out from solidfied material (b), passes through thermomechanical analyzer
(TMA) determine.
Determine device SSC-5200 (Seiko Instruments Inc (Seiko Instruments Inc.) system)
Condition determination load 20g/ 10 DEG C of heating per minute
Bending strength：Determined according to JIS (JIS) specification designation K7171.
The modulus of elasticity in static bending：Determined 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 bending is strong
Degree, in addition, solidfied material does not have crack yet, it is water white transparency.On the other hand, comparative example 1 is due to the cooperation of dendrimer
Amount is few, thus while with the low viscosity compared, but bending strength is poor.For comparative example 2, although with dendroid high score
The use level of son increases and bending strength increases, but viscosity becomes very high, and then solidfied material has been coloured to yellow.Comparing
In the solidfied material of example 3, in addition to generating crack, bending strength is also low, and solidfied material has been coloured to yellow.
According to the present invention, low viscosity and the easy composition epoxy resin of processing can be obtained, and intensity is high and coloring less,
Resistance to cracking and transparent excellent solidfied material.
Utilization possibility in industry
According to the present invention, the epoxy curing agent to form following composition epoxy resin, the epoxy resin can be obtained
Composition for low viscosity and is handled easily after blending, and the intensity of solidfied material is good；Thus, can obtain coloring less, resistance to open
Fragility and transparent excellent solidfied material.
Claims (10)
1. a kind of epoxy curing agent, it is characterised in that include 400~500mgKOH/g of polybasic acid anhydride and hydroxyl value branch
Shape macromolecule,
The polybasic acid anhydride is 4- methylhexahydrophthalic anhydrides or 3- methylhexahydrophthalic anhydrides and 4- methyl
The mixture of hexahydrophthalic anhydride,
The weight average molecular weight of the dendrimer is 1000~2000,
Relative to the parts by weight of polybasic acid anhydride 100, the dendrimer comprising 1~60 parts by weight.
2. epoxy curing agent according to claim 1, it is characterised in that the dendrimer is at 25 DEG C
Viscosity is below 10Pas.
3. epoxy curing agent according to claim 1, it is characterised in that the dendrimer is polyester.
A kind of 4. composition epoxy resin, it is characterised in that comprising epoxy resin, polybasic acid anhydride and hydroxyl value 400~
500mgKOH/g dendrimer,
The polybasic acid anhydride is 4- methylhexahydrophthalic anhydrides or 3- methylhexahydrophthalic anhydrides and 4- methyl
The mixture of hexahydrophthalic anhydride,
The weight average molecular weight of the dendrimer is 1000~2000,
Relative to the parts by weight of polybasic acid anhydride 100, the dendrimer comprising 1~60 parts by weight.
5. composition epoxy resin according to claim 4, it is characterised in that the dendrimer is at 25 DEG C
Viscosity is below 10Pas.
6. composition epoxy resin according to claim 4, it is characterised in that the dendrimer is polyester.
7. composition epoxy resin according to claim 4, it is characterised in that the epoxy resin is included in 1 molecule
Alicyclic epoxy resin with alicyclic skeleton and the epoxy radicals of more than 2.
8. composition epoxy resin according to claim 7, it is characterised in that the alicyclic epoxy resin is to be selected from
3 ', 4 '-epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylates, double (3,4- epoxycyclohexyl-methyls) adipate esters, second
At least one of alkene cyclohexene dioxide, hydrogenated bisphenol A diglycidyl ether resin.
9. a kind of solidfied material, it is characterised in that by making the composition epoxy resin described in any one of claim 4~8
Solidification is carried out to form.
10. a kind of optical semiconductor device, it is characterised in that by using the solidfied material sealing photosemiconductor member described in claim 9
Part forms.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008194808 | 2008-07-29 | ||
| JP2008-194808 | 2008-07-29 | ||
| JP2009-127596 | 2009-05-27 | ||
| JP2009127596 | 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 |
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| JP (1) | JP5522043B2 (en) |
| KR (1) | KR101636587B1 (en) |
| CN (2) | CN104693419B (en) |
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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 |
| KR20130100925A (en) * | 2010-06-30 | 2013-09-12 | 닛뽄 가야쿠 가부시키가이샤 | 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 |
| CN107431152B (en) * | 2015-03-30 | 2021-03-19 | 大日本印刷株式会社 | Battery packaging material, method for producing same, and battery |
| 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 |
| 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 |
| 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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| SE518592C2 (en) * | 2001-02-16 | 2002-10-29 | Perstorp Specialty Chem Ab | Process for preparing a carboxyl terminated dendritic polyester, powder coating composition prepared according to the method, and its use |
| US20060252892A1 (en) * | 2005-05-03 | 2006-11-09 | Basheer Rafil A | Hyperbranched polymer and cycloaliphatic epoxy resin thermosets |
| JP4876732B2 (en) * | 2006-04-26 | 2012-02-15 | 日立化成工業株式会社 | Epoxy resin composition, cured product thereof, and optical semiconductor device |
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| TWI464192B (en) | 2014-12-11 |
| TW201008970A (en) | 2010-03-01 |
| CN102112516A (en) | 2011-06-29 |
| JP5522043B2 (en) | 2014-06-18 |
| WO2010013638A1 (en) | 2010-02-04 |
| KR20110055481A (en) | 2011-05-25 |
| KR101636587B1 (en) | 2016-07-05 |
| JPWO2010013638A1 (en) | 2012-01-12 |
| CN104693419A (en) | 2015-06-10 |
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